Chemical and isotopic (<Superscript>18</Superscript>O/<Superscript>16</Superscript>O and D/<Superscript>1</Superscript>H) composition of groundwaters of central and southern Primorye

Groundwaters of Primorye, including its coastal areas, were studied during the past ten years. The macro-and microelement composition of more than 130 samples showed that shallow groundwaters of southern Primorye with pH ranging between 5.4 and 8.4 contain oxygen (up to 10 mg/l) and typically have a mixed ionic composition. The microelement variations reflect both the natural features of the host rocks and possible anthropogenic pollution in the most populated areas. No seawater intrusions were recognized in the study areas, which is confirmed by the chemical composition of the waters, the oxygen and hydrogen isotopic composition of the groundwaters, the atmospheric precipitation, and the coastal seawaters of Primorye. In spite of the variations of individual components, the quality of the groundwaters used for potable purposes is rather satisfactory as compared to the Russian and the World Health Organization standards. At the same time, taking into account the increase of various microelements and biogenic components in the waters, the monitoring and control of the water composition is strongly recommended to preserve their potable quality.     

Zinclipscombite,ZnFe<Stack><Subscript>2</Subscript><Superscript>3+</Superscript></Stack>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>2</Subscript>, a new mineral species

Zinclipscombite, a new mineral species, has been found together with apophyllite, quartz, barite, jarosite, plumbojarosite, turquoise, and calcite at the Silver Coin mine, Edna Mountains, Valmy, Humboldt County, Nevada, United States. The new mineral forms spheroidal, fibrous segregations; the thickness of the fibers, which extend along the c axis, reaches 20 μm, and the diameter of spherulites is up to 2.5 mm. The color is dark green to brown with a light green to beige streak and a vitreous luster. The mineral is translucent. The Mohs hardness is 5. Zinclipscombite is brittle; cleavage is not observed; fracture is uneven. The density is 3.65(4) g/cm³ measured by hydrostatic weighing and 3.727 g/cm³ calculated from X-ray powder data. The frequencies of absorption bands in the infrared spectrum of zinclipscombite are (cm^?1; the frequencies of the strongest bands are underlined; sh, shoulder; w, weak band) 3535, 3330sh, 3260, 1625w, 1530w, 1068, 1047, 1022, 970sh, 768w, 684w, 609, 502, and 460. The Mössbauer spectrum of zinclipscombite contains only a doublet corresponding to Fe³⁺ with sixfold coordination and a quadrupole splitting of 0.562 mm/s; Fe²⁺ is absent. The mineral is optically uniaxial and positive, ω = 1.755(5), ? = 1.795(5). Zinclipscombite is pleochroic, from bright green to blue-green on X and light greenish brown on Z (X > Z). Chemical composition (electron microprobe, average of five point analyses, wt %): CaO 0.30, ZnO 15.90, Al₂O₃ 4.77, Fe₂O₃ 35.14, P₂O₅ 33.86, As₂O₅ 4.05, H₂O (determined by the Penfield method) 4.94, total 98.96. The empirical formula calculated on the basis of (PO₄,AsO₄)₂ is (Zn_0.76Ca_0.02)_Σ0.78(Fe _1.72 ³⁺ Al_0.36)_Σ2.08[(PO₄)_1.86(AsO₄)_0.14]_Σ2.00(OH)_{1. 80} · 0.17H₂O. The simplified formula is ZnFe ₂ ³⁺ (PO₄)₂(OH)₂. Zinclipscombite is tetragonal, space group P4₃2₁2 or P4₁2₁2; a = 7.242(2) Å, c = 13.125(5) Å, V = 688.4(5) ų, Z = 4. The strongest reflections in the X-ray powder diffraction pattern (d, (I, %) ((hkl)) are 4.79(80)(111), 3.32(100)(113), 3.21(60)(210), 2.602(45)(213), 2.299(40)(214), 2.049(40)(106), 1.663(45)(226), 1.605(50)(421, 108). Zinclipscombite is an analogue of lipscombite, Fe²⁺Fe ₂ ³⁺ (PO₄)₂(OH)₂ (tetragonal), with Zn instead of Fe²⁺. The mineral is named for its chemical composition, the Zn-dominant analogue of lipscombite. The type material of zinclipscombite is deposited in the Mineralogical Collection of the Technische Universität Bergakademie Freiberg, Germany.     

EPR study of chromium-doped forsterite crystals: Cr<Superscript>3+</Superscript>(<Emphasis Type="Italic">M</Emphasis>1) with and without associated nearest-neighbor Mg<Superscript>2+</Superscript>(<Emphasis Type="Italic">M</Emphasis>2) vacancy

Electron paramagnetic resonance (EPR) study of single crystals of chromium-doped forsterite grown by the Czochralski method in two different research laboratories has revealed, apart from the known paramagnetic centers Cr³⁺(M1), Cr³⁺(M2) and Cr⁴⁺, a new center \textCr ³⁺ (M 1)-V_{\textMg ²⁺} (M 2) {\text{Cr}}^{ 3+ } (M 1){-}V_{{{\text{Mg}}^{ 2+ } }} (M 2) formed by a Cr³⁺ ion substituting for Mg²⁺ at the M1 structural position with a nearest-neighbor Mg²⁺ vacancy at the M2 position. For this center, the conventional zero-field splitting parameters D and E and the principal g values and A values of the ⁵³Cr hyperfine splitting have been determined as follows: D = 33.95(3) GHz, E = 8.64(1) GHz, g = [1.9811(2), 1.9787(2), 1.9742(2)], A = [51(3), 52(2), 44(3)] MHz. The center has been identified by comparing EPR spectra with those of the charge-uncompensated ion Cr³⁺(M1) and the ion pair Cr³⁺(M1)–Li⁺(M2) observed in forsterite crystals codoped with chromium and lithium. It has been found that the concentration of the new center decreases to zero, whereas that of the Cr³⁺(M1) and Cr³⁺(M1)–Li⁺(M2) centers increases with an increase of the Li content from 0 up to ~0.03 wt% (at the same Cr content ~0.07 wt%) in the melt. The known low-temperature luminescence data pertinent to the centers under consideration are also discussed.     

Cosmogenic radionuclide <Superscript>7</Superscript>Be concentration in seven species of lichens and its correlation with <Superscript>40</Superscript>K, <Superscript>137</Superscript>Cs and <Superscript>226</Superscript>Ra

In this work, accumulation of cosmogenic radionuclide ⁷Be in seven species of lichens was determined using HPGe detectors in autumn season. Ramsar city which is located in the north of Iran as one of the high-level natural radiation areas in the world was considered. Lichen species represented good potential in accumulation of ⁷Be radionuclide. The foliose species of Xanthoria parietina with the highest activity concentration value of 112.8 ± 1.8 Bq kg^?1 was introduced as bioindicator for accumulation of ⁷Be radionuclide. Cladonia rangiformis species has got minimum concentration of 64.5 ± 0.8 Bq kg^?1. Also from thallus morphology viewpoint, results showed that ⁷Be accumulation in foliose species is higher than in fruticose and crustose lichens species. Also there was relatively large positive correlation between ⁷Be and ²²⁶Ra activity concentrations in lichens species.     

Differential behavior of components of the <Superscript>238</Superscript>U-<Superscript>206</Superscript>Pb and <Superscript>235</Superscript>U-<Superscript>207</Superscript>Pb isotopic systems in polymineralic U ores

U-Pb systems were examined in samples (ranging from 4 to 10 cm³ in volume) of ore material taken from along a 3.5-m profile across a zone of U mineralization exposed in an underground mine at the Strel’tsovskoe U deposit in eastern Transbaikalia. The behaviors of two isotopic U-Pb systems (²³⁸U-²⁰⁶Pb and ²³⁵U-²⁰⁷Pb) are principally different in all samples from our profile. While the individual samples are characterized by a vast scatter of their T(²⁰⁶Pb/²³⁸U) age values (from 112 to 717 Ma), the corresponding T(²⁰⁷Pb/²³⁵U) values vary much less significantly (from 127 to 142 Ma) and are generally close to the true age of the U mineralization. The main reason for the distortion of the U-Pb system is the long-lasting (for tens of million years) migration of intermediate decay products in the ²³⁸U-²⁰⁶Pb(RD²³⁸U) in the samples. This process resulted in the loss of RD²³⁸U from domains with high U concentrations and the subsequent accommodation of RD²³⁸U at sites with low U concentrations. The long-term effect of these opposite processes resulted in a deficit or excess of ²⁰⁶Pb as the final product of ²³⁸U decay. The loss or migration of RD²³⁸U are explained by the occurrence of pitchblende in association with U oxides that have higher Si and OH concentrations than those in the pitchblende and a higher ⁺⁶U/⁺⁴U ratio. The finely dispersed character of the mineralization and the loose or metamict texture of the material are the principal prerequisites for RD²³⁸U loss and an excess of ²⁰⁶Pb in adjacent domains with low U concentrations. Domains with low U contents in the zone with U mineralization serve as geochemical barriers (because of sulfides contained in them) at which long-lived RD²³⁸U(²²⁶Ra, ²¹⁰Po, ²¹⁰Bi, and ²¹⁰Pb) were accommodated and subsequently caused an excess of ²⁰⁶Pb. The ²³⁵U-²⁰⁷Pb system remained closed because of the much briefer lifetime of the ²³⁵U decay products. This may account for the significant discrepancies between the T(²⁰⁶Pb/²³⁸U) and T(²⁰⁷Pb/²³⁵U) age values. RD²³⁸U was most probably lost via the migration of radioisotopes at the middle part and end of the ²³⁸U family (starting with ²²⁶Ra). The heavy Th, Pa, and U radioisotopes (²³⁴Th, ²³⁴Pa, ²³⁴U, and ²³⁰Th) that occur closer to the beginning of ²³⁸U decay, before ²²⁶Ra, only relatively insignificantly participated in the process. Our results show that the loss and migration of RD²³⁸U are, under certain conditions, the main (or even the only) process responsible for the distortion of the U-Pb system.     

<Superscript>226</Superscript>Ra, <Superscript>232</Superscript>Th and <Superscript>40</Superscript>K activities in soils of Cuihua Mountain National Geological Park,China

Gamma activity from the naturally occurring radionuclides namely, ²²⁶Ra, ²³²Th, the primordial radionuclide ⁴⁰K was measured in the soil of Cuihua Mountain National Geological Park, China using γ-ray spectrometry technique. The mean activity of ²²⁶Ra, ²³²Th and ⁴⁰K were found to be 27.2 ± 6.5, 43.9 ± 6.2 and 653.1 ± 127.6 Bq kg⁻¹, respectively. The concentrations of these radionuclides were compared with the typical world values and the average activities of Chinese soil. The radium equivalent activity, the air absorbed dose rate, the annual effective dose rate, and the external hazard index were evaluated and compared with the internationally approved values. All the soil samples have Ra_eq lower than the limit of 370 Bq kg⁻¹ and H _ex less than unity. The overall mean outdoor terrestrial gamma dose rate is 66.3 nGy h⁻¹ and the corresponding outdoor annual effective dose is 0.081 mSv.     

Detecting inter-aquifer leakage in areas with limited data using hydraulics and multiple environmental tracers,including <Superscript>4</Superscript>He, <Superscript>36</Superscript>Cl/Cl, <Superscript>14</Superscript>C and <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr

The investigation of regionally extensive groundwater systems in remote areas is hindered by a shortage of data due to a sparse observation network, which limits our understanding of the hydrogeological processes in arid regions. The study used a multidisciplinary approach to determine hydraulic connectivity between the Great Artesian Basin (GAB) and the underlying Arckaringa Basin in the desert region of Central Australia. In order to manage the impacts of groundwater abstraction from the Arckaringa Basin, it is vital to understand its connectivity with the GAB (upper aquifer), as the latter supports local pastoral stations and groundwater-dependent springs with unique endemic flora and fauna. The study is based on the collation of available geological information, a detailed analysis of hydraulic data, and data on environmental tracers. Enhanced inter-aquifer leakage in the centre of the study area was identified, as well as recharge to the GAB from ephemeral rivers and waterholes. Throughout the rest of the study area, inter-aquifer leakage is likely controlled by diffuse inter-aquifer leakage, but the coarse spatial resolution means that the presence of additional enhanced inter-aquifer leakage sites cannot be excluded. This study makes the case that a multi-tracer approach along with groundwater hydraulics and geology provides a tool-set to investigate enhanced inter-aquifer leakage even in a groundwater basin with a paucity of data. A particular problem encountered in this study was the ambiguous interpretation of different age tracers, which is attributed to diffusive transport across flow paths caused by low recharge rates.     

Granitoid magmatism of the Lermontovskaya and Vostok-2 tungsten ore-magmatic systems: U-Pb (SHRIMP) dating and isotope characteristics (<Superscript>3</Superscript>He/<Superscript>4</Superscript>He) of ores

U-Pb (SHRIMP) isotope dating of magmatic complexes of tungsten ore-magmatic systems (OMSs) resulted in a conclusion about the close age (103–105 Ma) of their formation in the magmatic rock masses from the Tatibinsk plutonic series whose location is controlled by the Sikhote-Alin’ strike-slip fault system. The OMSs are formed within the zones of strike-slip fault extensions (“windows”) dipping into the mantle, which establishes the conditions for the participation of deep fluids in the generation of melts at the level of crustal-mantle interaction. The new data from the study of the isotope composition of helium in the fluid inclusions showed that the content of mantle helium in ores of tungsten OMSs is approximately 10%.     

Results of <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar dating of phlogopites from kelyphitic rims around garnet grains (Udachnaya-Vostochnaya kimberlite pipe)

⁴⁰Ar/³⁹Ar dating of phlogopite from kelyphitic rims around garnet grains from the Udachnaya–Vostochnaya kimberlite pipe in the Sakha (Yakutia) Republic (Russia) revealed that when this mineral has contact with a kimberlite melt its age corresponds (within error limits) to that of the formation of the kimberlite pipe, thus indicating that the method may be used for dating kimberlites and related rocks. In mantle xenoliths, kelyphitic phlogopites rimming garnet grains partially lose radiogenic Ar, which results in a complex age spectrum. Rejuvenation of the K/Ar system in them is determined by the thermal impact of the kimberlite melt on captured rocks.     

Integrated stratigraphy and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar chronology of the Early to Middle Miocene Upper Freshwater Molasse in eastern Bavaria (Germany)

A detailed integrated stratigraphic study was carried out on middle Miocene fluvial successions of the Upper Freshwater Molasse (OSM) from the North Alpine Foreland Basin, in eastern Bavaria, Germany. The biostratigraphic investigations yielded six new localities thereby refining the OSM biostratigraphy for units C to E (sensu; Heissig, Actes du Congres BiochroM’97. Mem Trav EPHE, Inst Montpellier 21, 1997) and further improving biostratigraphic correlations between the different sections throughout eastern Bavaria. Radioisotopic ages of 14.55 ± 0.19 and 14.88 ± 0.11 Ma have been obtained for glass shards from the main bentonite horizon and the Ries impactite: two important stratigraphic marker beds used for confirming our magnetostratigraphic calibration to the Astronomical Tuned Neogene Time Scale (ATNTS04; Lourens et al. in Geologic Time Scale 2004, Cambridge University Press, 2004). Paleomagnetic analysis was performed using alternating field (AF) and thermal (TH) demagnetization methods. The AF method revealed both normal and reverse polarities but proofs to yield unreliable ChRM directions for the Puttenhausen section. Using the biostratigraphic information and radioisotopic ages, the magnetostratigraphic records of the different sections are tentatively correlated to the Astronomical Tuned Neogene Time Scale (ATNTS04; Lourens et al. in Geologic Time Scale 2004, Cambridge University Press, 2004). This correlation implies that the main bentonite horizon coincides to chron C5ADn, which is corroborated by its radioisotopic age of 14.55 Ma, whereas the new fossil locality Furth 460, belonging to OSM unit E, probably correlates to chron C5Bn.1r. The latter correlation agrees well with the Swiss Molasse locality Frohberg. Correlations of the older sections are not straightforward. The Brock horizon, which comprises limestone ejecta from the Ries impact, possibly correlates to C5ADr (14.581–14.784 Ma), implying that, although within error, the radioisotopic age of 14.88 ± 0.11 Ma is somewhat too old. The fossil localities in Puttenhausen, belonging to the older part of OSM unit C, probably coincide with chron C5Cn.2n or older, which is older than the correlations established for the Swiss Molasse. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

<Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar age of the porphyry Ca(Au) mineralization of the Elna deposit and its relation to magmatism (northeastern part of the Argun superterrane)

The Elna Cu(Au)–porphyry deposit is one of the typical ore objects in the northeastern margin of the Argun superterrane facing the Mongolia–Okhotsk foldbelt. Mineralization includes zones of argillization with fine quartz veins in granodiorite of the Elna massif. The geochronological ⁴⁰Ar/³⁹Ar studies of hydrothermal near-ore metasomatites and magmatic rocks of the deposit show that the age of host granitoids is 126 ± 2 Ma, which corresponds to the upper age boundary of granitoids from the Burinda Complex, whereas the age of overprinted hydrothermal processes is 122–117 Ma. The age of mineralization correlates well with the age of the thermal event in East Asia. An intense stage of magmatism including both volcanic and intrusive forms occurred in this period.     

Correlation of δ<Superscript>18</Superscript>O and initial<Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr ratios in Kirkpatrick basalt on Mt. Falla,transantarctic mountains

Theδ¹⁸O (SMOW) values of the Kirkpatrick Basalt (Jurassic) on Mt. Falla, Queen Alexandra Range, vary between +6.3‰ and +8.6‰ The apparent enrichment of these rocks in¹⁸O excludes the possibility that they were altered by interaction with aqueous solutions of meteoric origin. Theδ¹⁸O values of the flows correlate significantly with the initial⁸⁷Sr/⁸⁶Sr ratios and all major elements. These correlations confirm the hypothesis that the basalt magma was contaminated by rocks of the continental crust through which it was extruded. Estimates of the chemical composition of the basalt magma and the contaminant, based on extrapolations of the new oxygen data, generally confirm earlier estimates based on extrapolations of initial⁸⁷Sr/⁸⁶Sr ratios. The⁸⁷Sr/⁸⁶Sr ratio of the uncontaminated basalt was 0.7093 which indicates that magma may have originated by melting either in old Rb-enriched lithospheric mantle under Antarctica or in the overlying crust, or both.     

Measurement of marine productivity using <Superscript>15</Superscript>N and <Superscript>13</Superscript>C tracers: Some methodological aspects

Various experiments involving the measurement of new, regenerated and total productivity using ¹⁵N and ¹³C tracers were carried out in the Bay of Bengal (BOB) and in the Arabian Sea. Results from ¹⁵N tracer experiments indicate that nitrate uptake can be underestimated by experiments with incubation time <4 hours. Indirect evidence suggests pico- and nano-phytoplankton, on their dominance over microphytoplankton, can also influence the f-ratios. Difference in energy requirement for assimilation of different nitrogen compounds decides the preferred nitrogen source during the early hours of incubation. Variation in light intensity during incubation also plays a significant role in the assimilation of nitrogen. Results from time course experiments with both ¹⁵N and ¹³C tracers suggest that photoinhibition appears significant in BOB and the Arabian Sea during noon. A significant correlation has been found in the productivity values obtained using ¹⁵N and ¹³C tracers.     

Magnetic phase diagrams of Mg-, Fe-, (Cu + Ti)- and Cu-substituted braunite Mn<Superscript>2+</Superscript>Mn<Subscript>6</Subscript><Superscript>3+</Superscript>SiO<Subscript>12</Subscript>

 The magnetic behavior of the Jahn-Teller structure braunite, (Mn²⁺ _1−yM _y )(Mn³⁺ _{6− x} M_x)SiO₁₂, is strongly influenced by the incorporation of elements substituting manganese. Magnetic properties of well-defined synthetic samples were investigated in dependence on the composition. The final results are presented in magnetic phase diagrams. To derive the necessary data, ac susceptibility and magnetization of braunites with the substitutional elements M = Mg, Fe, (Cu+Ti) and Cu were measured. Whereas the antiferromagnetic ordering temperature, T _N , of pure braunite is hardly affected by the substitution of nonmagnetic Mg, it is rapidly suppressed by the substitution of magnetic atoms at the Mn positions. Typically for a concentration (x, y) ≥ 0.7 of the substituted elements, a spin glass phase occurs in the magnetic phase diagrams. Additionally, for the braunite system with Fe³⁺ substitutions, we observe in the concentration range 0.2 < x< 0.7 a double transition from the paramagnetic state, first to the antiferromagnetic state, followed by a transition to a spin glass state at lower temperatures. The unusual change of the magnetic properties with magnetic substitution at the Mn positions is attributed to the peculiar antiferromagnetic structure of braunite, which has been resolved recently. Received: 19 April 2001 / Accepted: 6 September 2001