俄罗斯Kurile-Kamchatka地区安山质熔体的成分、挥发分组成和微量元素

Melt inclusions in minerals from some volcanoes of the Kurile-Kamchatka region were examined.The studied basaltic andesites and andesites were sampled from volcanoes of the Central Kamchatka depression(Shiveluch and Bezymyannyi),Eastern Kamchatka volcanic belt(Avachinskii and Karymskii),and Iturup Island,Southern Kuriles(Kudryavyi).Basalts of the 1996 eruption of the Karymskii volcanic center and dacites of Dikii Greben'volcano,Southern Kamchatka were also studied.More than 260 melt inclusions from 31 rock samples were homogenized,and quenched glasses were analyzed using electron and ion microprobes.The compositions of melt inclusions in andesitic phenoerysts vary in silica contents from 56 to 80wt%.Al_2 O_3 ,FeO,MgO,CaO decrease and Na_2O and K_2O increase with increasing SiO_2.Many inclusions(about 80% )are dacitic or rhyolitic.However,the compositions of silicic glasses(>65wt% SiO_2)in andesites significantly differ in TiO2,FeO,MgO,CaO,and K_2O contents from those in dacites and rhyolites.High-potassium melts(K_2O 3.8～6.8wt% )with various SiO_2 from 51.4 to 77.2wt% were found in minerals of all volcanoes studied.This indicates a contribution of a component selectively enriched in potassium to magmas of the whole region.A great compositional diversity of melt inclusions in plagioelase phenocrysts from the Bezymyannyi andesites suggests a complex history of plagioclase crystallization and magma evolution in the andesite formation.Melts from different volcanoes strongly vary in volatile contents.The highest H_2O contents are found in the melts from Shiveluch(3.0～7.2wt%,4.7wt% on average)and Avachinskii (4.7～4.8wt%);while those are lower in melts of Kudryavyi(0.1～2.6wt% ),Dikii Greben'(0.4～1.8wt%),and Bezymyannyi (<1wt%).Chlorine contents are also variable.The lowest values are found in the Bezymyannyi melts(0.09wt% on average),the highest Cl contents are typical of melt inclusions in minerals from the Karymskii andesites(0.26wt% on average).The melts from Avachinskii,Dikii Greben',Kudryavyi,and Shiveluch show intermediate Cl contents(0.13～0.20wt% ).The pressure of 350～1600 bar determined by CO_2 fluid inclusions in plagioclase from the Shiveluch andesites suggests a magma chamber at a depth of 1.5～6 km. Concentrations of 17 elements were determined in glasses of melt inclusions in plagioclases from five volcanoes(Avachinskii, Bezymyannyi,Dikii Greben',Kudryavyi,and Shiveluch).The studied melts show similar trace-element patterns with Nb and Ti minima and B,K,Be,and Li maxima.The melts are close to typical island arc magmas by Sr/Y,La/Yb,K/Ti,and Ca/St ratios, and have some specific regional geochemical features.REE patterns sensitive to degree of magma differentiation indicate that Kudryavyi magmas are most primitive,while Shiveluch magmas are most evolved.     

Chemical composition,volatile components,and trace elements in the melts of the Gorely volcanic center,southern Kamchatka: Evidence from inclusions in minerals

Melt inclusions in olivine and plagioclase phenocrysts from rocks (magnesian basalt, basaltic andesite, andesite, ignimbrite, and dacite) of various age from the Gorely volcanic center, southern Kamchatka, were studying by means of their homogenization and by analyzing the glasses in 100 melt inclusions on an electron microprobe and 24 inclusions on an ion probe. The SiO₂ concentrations of the melts vary within a broad range of 45–74 wt %, as also are the concentrations of other major components. According to their SiO₂, Na₂O, K₂O, TiO₂, and P₂O₅ concentrations, the melts are classified into seven groups. The mafic melts (45–53 wt % SiO₂) comprise the following varieties: potassic (on average 4.2 wt % K₂O, 1.7 wt % Na₂O, 1.0 wt % TiO₂, and 0.20 wt % P₂O₅), sodic (3.2% Na₂O, 1.1% K₂O, 1.1% TiO₂, and 0.40% P₂O₅), and titaniferous with high P₂O₅ concentrations (2.2% TiO₂, 1.1% P₂O₅, 3.8% Na₂O, and 3.0% K₂O). The melts of intermediate composition (53–64% SiO₂) also include potassic (5.6% K₂O, 3.4% Na₂O, 1.0% TiO₂, and 0.4% P₂O₅) and sodic (4.3% Na₂O, 2.8% K₂O, 1.3% TiO₂, and 0.4% P₂O₅) varieties. The acid melts (64–74% SiO₂) are either potassic (4.5% K₂O, 3.6% Na₂O, 0.7% TiO₂, and 0.15% P₂O₅) or sodic (4.5% Na₂O, 3.1% K₂O, 0.7% TiO₂, and 0.13% P₂O₅). A distinctive feature of the Gorely volcanic center is the pervasive occurrence of K-rich compositions throughout the whole compositional range (silicity) of the melts. Melt inclusions of various types were sometimes found not only in a single sample but also in the same phenocrysts. The sodic and potassic types of the melts contain different Cl and F concentrations: the sodic melts are richer in Cl, whereas the potassic melts are enriched in F. We are the first to discover potassic melts with very high F concentrations (up to 2.7 wt %, 1.19 wt % on average, 17 analyses) in the Kuriles and Kamchatka. The average F concentration in the sodic melts is 0.16 wt % (37 analyses). The melts are distinguished for their richness in various groups of trace elements: LILE, REE (particularly HREE), and HFSE (except Nb). All of the melts share certain geochemical features. The concentrations of elements systematically increase from the mafic to acid melts (except only for the Sr and Eu concentrations, because of active plagioclase fractionation, and Ti, an element contained in ore minerals). The paper presents a review of literature data on volcanic rocks in the Kurile-Kamchatka area in which melt inclusions with high K₂O concentrations (K₂O/Na₂O > 1) were found. K-rich melts are proved to be extremely widespread in the area and were found on such volcanoes as Avachinskii, Bezymyannyi, Bol’shoi Semyachek, Dikii Greben’, Karymskii, Kekuknaiskii, Kudryavyi, and Shiveluch and in the Valaginskii and Tumrok Ranges.     

Natural concentrations of major and trace elements in some Norwegian bedrock groundwaters

Twenty-eight groundwater samples have been collected from boreholes in bedrock aquifers in Nord Trøndelag (Central Norway), the Hvaler archipelago and other areas around Oslofjord (South-eastern Norway). A clear relationship is demonstrated between many chemical parameters and lithology or geographical location. The parameters electrical conductivity, Cl⁻, SO₄²⁻, F⁻, Na, Al, Fe, Be, Bi, Cd, Cu, La, Mo, Pb, Th, Tl, U, Y, Zn, Zr, B, Rn, and Si have generally higher values in the Iddefjord Granite of Hvaler, while pH, alkalinity, Ca, Mg, Cs, Rb, and Sr are highest in Trøndelag. Several parameters such as F⁻, Na, Fe, U, Rn and possibly Al exceed drinking water norms on Hvaler. Measured values of the analyzed parameters compare well (except F⁻) with the Dutch “A” (background) values, developed for assessment of anthropogenic contamination. The authors warn, however, against uncritical use of “norms” developed in countries with other dominant lithologies than Norway.     

Chemical composition,volatile components,and trace elements in melts of the Karymskii volcanic center,Kamchatka, and Golovnina volcano,Kunashir Island: Evidence from inclusions in minerals

Melt inclusions were examined in phenocrysts in basalt, andesite, dacite, and rhyodacite from the Karymskii volcanic center in Kamchatka and dacite form Golovnina volcano in Kunashir Island, Kuriles. The inclusions were examined by homogenization and by analyzing glasses in more than 80 inclusions on an electron microscope and ion microprobe. The SiO₂ concentrations in the melt inclusions in plagioclase phenocrysts from basalts from the Karymskii volcanic center vary from 47.4 to 57.1 wt %, these values for inclusions in plagioclase phenocrysts from andesites are 55.7–67.1 wt %, in plagioclase phenocrysts from the dacites and rhyodacites are 65.9–73.1 wt %, and those in quartz in the rhyodacites are 72.2–75.7 wt %. The SiO₂ concentrations in melt inclusions in quartz from dacites from Golovnina volcano range from 70.2 to 77.0 wt %. The basaltic melts are characterized by usual concentrations of major components (wt %): TiO₂ = 0.7–1.3, FeO = 6.8–11.4, MgO = 2.3–6.1, CaO = 6.7–10.8, and K₂O = 0.4–1.7; but these rocks are notably enriched in Na₂O (2.9–7.4 wt % at an average of 5.1 wt %, with the highest Na₂O concentration detected in the most basic melts: SiO₂ = 47.4–52.0 wt %. The concentrations of volatiles in the basic melts are 1.6 wt % for H₂O, 0.14 wt % for S, 0.09 wt % for Cl, and 50 ppm for F. The andesite melts are characterized by high concentrations (wt %) of FeO (6.5 on average), CaO (5.2), and Cl (0.26) at usual concentrations of Na₂O (4.5), K₂O (2.1), and S (0.07). High water concentrations were determined in the dacite and rhyodacite melts: from 0.9 to 7.3 wt % (average of 15 analyses equals 4.5 wt %). The Cl concentration in these melts is 0.15 wt %, and those of F and S are 0.06 and 0.01 wt %, respectively. Melt inclusions in quartz from the dacites of Golovnina volcano are also rich in water: they contain from 5.0 to 6.7 wt % (average 5.6 wt %). The comparison of melt compositions from the Karymskii volcanic center and previously studied melts from Bezymyannyi and Shiveluch volcanoes revealed their significant differences. The former are more basic, are enriched in Ti, Fe, Mg, Ca, Na, and P but significantly depleted in K. The melts of the Karymskii volcanic center are most probably less differentiated than the melts of Bezymyannyi and Shiveluch volcanoes. The concentrations of water and 20 trace elements were measured in the glasses of 22 melt inclusions in plagioclase and quartz from our samples. Unusually high values were obtained for Li concentrations (along with high Na concentrations) in the basaltic melts from the Karymskii volcanic center: from 118 to 1750 ppm, whereas the dacite and rhyolite melts contain 25 ppm Li on average. The rhyolite melts of Golovnina volcano are much poorer in Li: 1.4 ppm on average. The melts of the Karymskii volcanic center are characterized by relative minima at Nb and Ti and maxima at B and K, as is typical of arc magmas.     

Chemical composition,volatile components,and trace elements in the magmatic melt of the Kurama mining district,Middle Tien Shan: Evidence from the investigation of inclusions in quartz

Melt and fluid inclusions were investigated in six quartz phenocryst samples from the igneous rocks of the extrusive (ignimbrites and rhyolites) and subvolcanic (granite porphyries) facies of the Lashkerek Depression in the Kurama mining district, Middle Tien Shan. The method of inclusion homogenization was used, and glasses from more than 40 inclusions were analyzed on electron and ion microprobes. The chemical characteristics of these inclusions are typical of silicic magmatic melts. The average composition is the following (wt %): 72.4 SiO₂, 0.06 TiO₂, 13.3 Al₂O₃, 0.95 FeO, 0.03 MnO, 0.01 MgO, 0.46 CaO, 3.33 Na₂O, 5.16K₂O, 0.32 F, and 0.21 Cl. Potassium strongly prevails over sodium in all of the inclusions (K₂O/Na₂O averages 1.60). The average total of components in melt inclusions from five samples is 95.3 wt %, which indicates a possible average water content in the melt of no less than 3–4 wt %. Water contents of 2.0 wt % and 6.6 wt % were determined in melt inclusions from two samples using an ion microprobe. The analyses of ore elements in the melt inclusions revealed high contents of Sn (up to 970 ppm), Th (19–62 ppm, 47 ppm on average), and U (9–26 ppm, 18 ppm on average), but very low Eu contents (0.01 ppm). Melt inclusions of two different compositions were detected in quartz from a granite porphyry sample: silicate and chloride, the latter being more abundant. In addition to Na and K chlorides, the salt inclusions usually contain one or several anisotropic crystals and an opaque phase. The homogenization temperatures of the salt inclusions are rather high, from 680 to 820°C. In addition to silicate inclusions with homogenization temperatures of 820–850°C, a primary fluid inclusion of aqueous solution with a concentration of 3.7 wt % NaCl eq. and a very high density of 0.93 g/cm³ was found in quartz from the ignimbrite. High fluid pressure values of 6.5–8.3 kbar were calculated for the temperature of quartz formation. These estimates are comparable with values obtained by us previously for other regions of the world: 2.6–4.3 kbar for Italy, 3.7 kbar for Mongolia, 3.3–8.7 kbar for central Slovakia, and 3.3–9.6 kbar for eastern Slovakia. Unusual melt inclusions were investigated in quartz from another ignimbrite sample. In addition to a gas phase and transparent glass, they contain spherical Feoxide globules (81.2 wt % FeO) with high content of SiO₂ (9.9 wt %). The globules were dissolved in the silicate melt within a narrow temperature range of 1050–1100°C, and the complete homogenization of the inclusions was observed at temperatures of 1140°C or higher. The combined analysis of the results of the investigation of these inclusions allowed us to conclude that immiscible liquids were formed in the high-temperature silicic magma with the separation of iron oxide-dominated droplets.     

Sources and geodynamic environments of formation of Vendian-Early Paleozoic magmatic complexes in the Daribi range,Western Mongolia

Rock complexes composing the Daribi Range were produced in Late Vendian, Early Cambrian, and Early Paleozoic suprasubduction systems. All of the studied mafic and ultramafic magmatic mantle rocks (the post-Vendian ophiolite complex, Early Cambrian pillow basalts, and Early Paleozoic picrobasalts of the sill-dike complex) have geochemical characteristics typical of early evolutionary episodes of island arcs: low LILE concentrations, horizontal REE patterns or patterns close to those of N-MORB, and HFSE minima. The magmas were derived from depleted mantle sources of variable isotopic composition with ?_Nd(T) from +2.5 to +10. The Early Paleozoic rocks of the sill-dike complex were likely produced by a complicated interaction of melts derived from different sources. The rocks of group 1 resulted from the mixing of low-K picrite and tonalite melts. The picrite melts with ?_Nd(T) from +6 to +8 were melted out of garnet lherzolite in the mantle wedge. The tonalite melts with ?_Nd(T) = ?3 seem to have been formed by the partial melting of mafic oceanic rocks of a subducted slab or the bottom of an island arc. The trondhjemite melts of group 2 with ?_Nd(T) varying from 2.5 to 7.5 could be formed via the melting of subducted metapelites or amphibolites with low sulfide concentrations. Massifs of sodic Early Paleozoic granites also occur elsewhere in western Mongolia, Tuva, and the Altai territory. The generation of sodic silicic melts was likely a common process in supra-subduction systems in CAFB. The potassic granites (group 4) could be formed by the melting of subducted pelites or by the fractionation of mantle magmas. The genesis of the basaltic andesites (group 5) was likely related to Mesozoic-Cenozoic intraplate processes.     

Comparison of major,volatile, and trace element contents in the melts of mid-ocean ridges on the basis of data on inclusions in minerals and quenched glasses of rocks

Using our database on major, trace, and volatile element contents in melt inclusions in minerals and quenched glasses of volcanic rocks reported in the literature, we compared the mean contents of 71 chemical elements in melts from the mid-ocean ridges (MORB) of the Atlantic, Pacific, and Indian oceans and determined the mean MORB composition for all the oceans of the Earth (global MORB composition). Mean ratios of incompatible trace and volatile components (H₂O/Ce, K₂O/Cl, Nb/U, Ba/Rb, Ce/Pb, Nb/U, etc.) were calculated for magmatic melts from all the oceans. Variations of these parameters were estimated, and significant differences between the melts of the Atlantic and Pacific oceans were established.     

Impact of historical metalworks on the concentrations of major and trace elements in sediments: a case study in Finland

The concentrations of major and trace elements were determined (aqua regia leach and ICP-AES analyses) in stream, lake and dredged sediments downstream of the historical Antskog iron- and copperworks, S.Finland. The levels of Ag, Cd, Cu, Pb and Zn are highly elevated in all studied sediment types: roughly half of the studied lake-sediment samples contain >5 ppm Ag, >15 ppm Cd, >0.1% Cu, >0.1% Pb and >0.3% Zn. In the dredged sediment material located onshore, the concentrations of Ag, Cu and Pb are comparable to those in the polluted lake-sediment samples, while in stream sediments elevated metal concentrations are found especially in samples characterised by high concentrations of organic material. The source of the elevated metal concentrations is the historical metalworks at Antskog, mainly the copperworks of the 19th century. Compared to the limit values for contaminated soils in Finland, the concentrations of Cu, Pb and Zn are on average elevated by factors >10 in the polluted horizons of lake sediments, >5 in the dredged sediment located onshore and >2 at the most heavily contaminated site in the stream. Since the surface waters in the area are used for agricultural purposes and for various leisure activities, it is necessary to make further detailed investigations into the extent of the metal pollution and to determine species, mobility and bioavailability of the metals.     

Tendencies in the distribution and hypotheses of the genesis of condensed naphthides in magmatic rocks from various geodynamic environments

Literature data suggest that concentrated naphthides (CN)—bitumen and oil—can occur in intrusive and volcanic rocks of various silicity and alkalinity whose age ranges from the Proterozoic to Recent. The qualitative composition of heavy (high-molecular) hydrocarbons (HHC) in CN is the same in various rocks: heavy alkanes, polycyclic aromatic hydrocarbons (PAH), oxygen-bearing derivatives of hydrocarbons, etc. The presence of CN in rock-forming minerals in magmatic rocks and pegmatites confirms that CN condensed during the epimagmatic stage, and the molecular mass of the CN, for example, in the Khibina alkaline massif decreased with decreasing temperature simultaneously with the evolution of its mineral assemblages. The synthesis of CN continues during the hydrothermal stage, but high-temperature associations of HHC gave way during this stage to low-temperature ones. During all evolutionary stages of magmatic and related processes, the contents of CN are correlated with those of trace elements, which likely occur as organoelement compounds (OEC). Hypotheses of endogenic and exogenic genesis of CN in magmatic rocks are discussed. The endogenic hypotheses include HHC synthesis from inorganic gases and light hydrocarbons (HC) on catalytic minerals. The fact that HHC and CN occur in mantle xenoliths and high-pressure minerals and the results of experimental and thermodynamic modeling are discussed as supporting the hypothesis of the mantle genesis of CN in magmatic rocks. The metastable ascent of gaseous HHC, the low oxygen fugacity, and the high alkalinity of the melts could be favorable for the partial preservation of HHC in these rocks at crustal depth levels. Endogenic CN can serve as a nutrient medium for microorganisms in the upper lithosphere. Exogenic hypotheses for the genesis of HHC in magmatic rocks assume that the melts should have assimilated sedimentary rocks rich in organic matter and that biogenic oil could be transported from sedimentary reservoirs to magmatic rocks. An important role in determining the genesis of CN in magmatic rocks is played by endogenic and biogenic markers.     

Concentration of ore elements in magmatic melts and natural fluids as deduced from data on inclusions in minerals

Based on intergration of the published data on composition of inclusions in minerals and quenched glasses, the mean concentrations of 24 ore elements have been calculated for magmatic silicate melts formed in main geodynamic settings of the Earth and in natural fluids. The mean glass compositions normalized to the primitive mantle correlate with the partition coefficient between olivine and the basic melt. It is established that the degree of enrichment in ore elements depending on geodynamic setting is controlled by various contribution of fluids to the element transfer and accumulation. The ratios of element contents in each geodynamic setting to the mean concentrations of elements over all settings in the Earth have been calculated.     

The association of major,minor and trace inorganic elements with lignites. I. Experimental approach and study of a North Dakota lignite

Lignites resemble peats, the precursors of coals, in containing many carboxylic acid and other functional groups. Consequently much of the relatively small amount of inorganic matter in lignites is present as cations in carboxylates and in chelated coordination complexes, and not only as distinct mineral phases. Consequently the distribution of inorganic matter in lignites will be influenced by the structure of the organic matter, as well as by microbial processes in peats and the geochemical processes involving erosion of rocks and transport of mineral grains and cations in solution. The objective of this study was to seek information on the distribution of major, minor and trace elements in different forms of combination, and in particular to document organic/inorganic interactions in coal formation. Study of the first of five lignites is reported here. The coal (from the Hagel seam in North Dakota) was separated into five fractions by float/ sink methods, and the fractions were further separated into an ammonium acetate extract, an HCl extract and an insoluble residue. Analysis of the fractions (by atomic absorption, plasma arc emission, emission spectroscopy and neutron activation) was found to give much information on how elements were combined in the coals. Results of the fractionation indicate that Ca, Mg, Na, K, Sr, Ba and Mn were present largely or partly in ion-exchangeable form; appreciable amounts of K (illite), Ba (sulfate, carbonate) and Mn were also present in mineral phases. Some Al appeared to be present in organic association. Ti often occurs in sediments by substitution in clays, but we infer that substantial amounts are present here in both acidsoluble and acid-insoluble organic chelates. The considerable enrichment of a number of elements in the fractions of lowest specific gravity suggests that Be, Sc, Cr, Y, Yb, V, Ni, Cu and Zn are associated primarily or partly with the organic matter. The extent to which these elements are associated with the organic matter in this lignite is much greater than it is with the bituminous coals studied by others.     

Isotopic relationships of volatile and lithophile trace elements in continental ultramafic xenoliths

The concentrations and isotopic compositions of Sr, Nd, Pb, He and C have been determined for suites of xenoliths from Bullenmerri (Australia), Ichinomegata (Japan), Geronimo (Arizona), and East Africa. The wehrlites and pyroxenites from Bullenmerri have Sr, Nd and Pb isotopic compositions that are generally similar to those found for alkali basalts in the region. The spinel lherzolites, in contrast, have higher ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb and lower ¹⁴³Nd/¹⁴⁴Nd ratios. Whereas the isotopic compositions of He are generally within the range of mid-ocean-ridge basalts (MORB) and do not covary with those of other trace elements, there is an apparent correlation between the ¹³C/¹²C and ¹⁴³Nd/¹⁴⁴Nd ratios for each of the two petrologic groups. These relationships, if substantiated for other xenolith suites, greatly limit the possible mechanisms for generating lithophile and volatile isotopic variations in the continental lithosphere. The helium isotopic compositions for all of the xenoliths fall within the range for MORB. This includes those from Ichinomegata, suggesting that the lower ³He/⁴He ratios found for He sampled at the surface at subduction zones result from mixing mantle He with near-surface crustal He rather than with subducted radiogenic He. Measured C isotopic compositions (relative to Peedee belemnite) for the Ichinomegata xenoliths include values that are both lighter and heavier than those in MORB, and are compatible with contributions from subducted carbon. The Nd and Sr isotopic compositions of the Ichinomegata xenoliths exhibit a correlation over a substantially greater range of values than typically observed for other light-rare-earth-element (LREE)-depleted xenoliths, and include more radiogenic Sr and less radiogenic Nd compositions. The carbon isotopic compositions found for the East African and Geronimo xenoliths extend to values that are lighter than those typically found for MORB.     

梅田矿区岩浆热变煤中微量元素分布特征

梅田矿区主采煤层－龙谭组１２号煤层主要是受矿区北部骑田岭花岗岩侵入体影响的典型岩浆热液变质无烟煤,煤的变质指标如挥发分和镜质组反射率Ｒ＾０（ｍａｘ）等与岩体有密切关系。本次研究按距离岩体由近而远采集了一系列煤样,运用中子活化（ＩＮＡＡ）和微区分析等测试手段研究了样品中近４０种微量元素的分布特征,结果表明：（１）Ａｓ,ｄ,Ｈｇ,Ｐｂ,Ｓｅ等对人体有毒元素在煤中的质量分数较地壳克拉克值高数倍至数十倍,     

Distribution of major and trace elements in La Luna Formation, Southwestern Venezuelan Basin

The La Luna Formation (Maraca section), Maracaibo Basin, was studied by means of V and Ni analysis of the bitumen, total organic carbon (TOC), total sulfur (St), major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, and Zn), and electron microprobe analysis (EPMA) of the whole rock, and St, major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, Zn, Mo, Ba, U, Th) and rare earth elements (La, Ce, Nd, Sn, Eu, Th, Yb, Lu) of the carbonate-free fraction. The results are discussed based on the organic and inorganic association of trace elements and their use as paleoenvironmental indicators of sedimentation. An association between V and organic matter is suggested by means of correlation between V and Ni vs. TOC, the use of EPMA (whole rock) and V and Ni concentrations (carbonate-free fraction), whereas Ni is found in the organic matter and the sulfide phase. Fe is present as massive and framboidal pyrite, whereas Zn precipitates into a separate phase (sphalerite), and Ni, Cu and, in some cases, Zn, can be found as sulfides associated with pyrite. Concentrations of V and Ni (bitumen), TOC, St, V, Ni, Cr, Cu and Zn (whole rock), U, Th, Mo (carbonate-free fraction) are indicative of changes in the dysoxic sedimentation conditions in the chert layers (TOC, St, V, Ni, Cu and low Zn and V/Cr <4) to euxinic anoxic conditions in the argillaceous limestone (TOC, St, V, Ni, Cu and high Zn and V/Cr >4). In the sequence corresponding to the argillaceous limestone, variations in the concentrations of TOC, St, V, Ni, Zn, Cu and Cr (whole rock) can be observed, also suggesting variable sedimentation conditions. The following is proposed: (i) sedimentation intervals under euxinic conditions associated with high contribution and/or preservation of organic matter, allowing a high concentration level of V and Ni in the organic phase and the accumulation of Cu, Zn and Ni (in a smaller proportion) in the sulfide phase; (ii) sedimentation intervals under anoxic conditions and in the presence of relatively lower H₂S, which allowed lower concentrations of V and Ni in the organic phase and higher concentrations of Cu, Zn, and Ni in the sulfide phase. Rare earth elements (REE) concentrations exhibit a marked increase in Ce, Nd, Sm, Eu, Y and Lu for the QM-3 interval, relative to Post-Archean Average Shale (PAAS). REE enrichment in shales has been related to the presence of phosphate minerals such as monazite or apatite. However, these minerals were not detected through XRD or EPMA in the whole rock or in the carbonate-free fraction. The association of REE with organic matter is suggested due to the absence of phosphate minerals, although assessment of these elements require further analysis.     

Migration and contamination of major and trace elements in groundwater of Madras city,India

Groundwater samples collected from both open and bore wells in an area of about 270 km² from Madras City, India, have been analyzed for major ions (HCO₃, Cl, Si, Na, Ca, and Mg) and trace elements (As, Se, B, V, Cr, Fe, Co, Pb, Cu, Zn, Cd, Mn, Ni, Mo, and Ba). The study reveals that the quality of potable water has deteriorated to a large extent. Seawater intrusion into the aquifer has been observed in nearly 50 percent of the study area. The toxic elements (As and Se) have already exceeded the maximum permissible limits of drinking water in almost the entire city. A positive correlation of As and Se with other toxic metals such as V, Cr, Fe, B, etc., indicates that all these elements are anthropogenic in origin. Applying multivariate analysis, the source for trace elements in groundwater has been grouped into two major factors: pollution and mobilization factors. The groundwater in the study area is largely contaminated by organic effluents and reflects the intensity of pollution caused by the overlying soil sediment and rapid infiltration of the pollutants.     

Distribution of major, minor and trace elements in Hat Creek Deposit No. 2, British Columbia, Canada

The major-, minor- and trace-element contents of coals from Hat Creek No. 2 deposit, British Columbia, are determined using INAA and inductively coupled plasma emission spectrometry (boron only).

Al, Cr, Fe, Mn and Na were found to be inorganically bound in the coal while As, B and S are associated with the organic fraction of the coal. The rare-earth element concentrations in the coal are variable, however, the LREE/HREE ratio decreases from base to the top of the deposits. Many elements show little variation in concentration with depth; however, the gradual increase of As and S with depth appears to be rank related and indicative of progressive decrease in porosity with increasing rank.

Concentrations of B and Cr are sensitive to the environment of coal deposition, with coal deposited in a freshwater environment (Hat Creek No. 2 deposit), having low B and high Cr compared with more brackish coals.     

Composition and variation of major and trace elements in Croatian bottled waters

Within the framework of the Pan-European project about the geochemistry of bottled mineral waters in Europe launched in 2007 by the European Geological Surveys (EGS) Geochemistry Expert Group fourteen brands of bottled natural waters from Croatia of both mineral and spring types were evaluated for getting more coherent spatial information about the natural variation of element concentration in bottled waters found at the European market. Results of chemical analysis show that not a single one out of fourteen analyzed bottled waters from Croatia exceeds the Croatian water standards sanctioning thereby their suitability for human consumption. Also, statistical tests performed for 41 analytes (including pH and EC) clearly show that the water chemistry is in a high degree of conformity with regional geology, depending on structural, stratigraphic and, above all, lithological diversity of aquifers. Thus Dinaric and Pannonian parts of Croatia differ largely with regard to their water types: Dinaric region is completely lacking mineral water types while, on the other side, in the Pannonian region even the spring waters show stronger mineralization in comparison with their Dinaric counterparts. Typically, all natural waters from Croatia bear the bicarbonate (HCO₃) signature. However, Ca–Mg cation pair combination is characteristic of spring waters while Na–K dominates in the mineral waters.