Loss of 40Ar(rad) from leucite-bearing basanite at low temperature: implications on K/Ar dating.

The Bakony-Balaton Highland Volcanic Field (BBHVF) is located in the central part of Transdanubia, Pannonian Basin, with over 50 alkali basaltic volcanoes. The basanite plug of Hegyestu erupted in the first phase of volcanic activity. K/Ar and Ar/Ar ages were published for the BBHVF. K/Ar and Ar/Ar ages of the leucite-bearing basanite of Hegyestás were conflicting. This is caused by the special Ar retention feature of leucite in this basanite. K/Ar ages measured in the usual way were 25–45% younger, but after HCl treatment of the rock, or after reducing the baking temperature of the argon extraction line from 250°C to 150°C, they became similar to the Ar/Ar ages. All Ar/Ar determinations were performed after HF treatment. HCl treatment dissolved olivine, nepheline, leucite, magnetite and from 1-1 sample analcime or calcite. K dissolution studies from different locations of Hegyestü have shown that K content is mostly ≈2%, but it may decrease to ≈0.3%. HCl treatment dissolved 28.0–63.5% of the K content. The calculated K concentration for the dissolved part of samples with ~2%K was 4.02-6.42%: showing that leucite is responsible for the low temperature loss of ⁴⁰Ar(rad). Ar may release at low temperature from very finegrained mineral, or when the Ar release mechanism changes. A ⁴⁰Ar(rad) degassing spectrum has been recorded in the 55–295°C range of baking temperature and the data were plotted in the Arrhenius diagram. The diagram shows that a change of the structure in the 145–295°C range caused the loss of ⁴⁰Ar(rad). On fractions of HCl treated rock 7.56±0.17 Ma isochron K/Ar age has been determined. This is regarded as minimum age of eruption and it is similar to the Ar/Ar isochron age (7.78±0.07 Ma).     

Distribution and isotope composition of nitrogen in Bay of Quinte (Lake Ontario) sediments

The concentrations and isotopic compositions of the various forms of nitrogen in silty clay sediments from the Bay of Quinte (Lake Ontario) have been determined. The total organic-N content is high throughout the sediment profiles and generally decreases with depth. On the contrary, exchangeable NH⁺₄-N concentration is quite low and tends to increase with depth in two out of three sediment cores examined. The concentration of non-exchangeable NH⁺₄-N and the 6 N HCl hydrolyzable NH⁺₄-N are relatively constant with depth. Among the N fractions analyzed, the exchangeable NH⁺₄-is most enriched in ¹⁵N. In most cases, the δ ¹⁵ N values of the N fractions remain relatively constant with sediment depth. There is no apparent correlation of δ ¹⁵ N values with the N concentration for any of the individual N fractions. The observed ranges in the δ ¹⁵ N values are: exchangeable NH⁺₄, + 5–+10‰; 6 N HCl hydrolyzable total N and 6 N HCl hydrolyzable NH⁺₄-N, + 3.5–+5.5‰.     

Comparison of groundwater recharge estimation methods for the semi-arid Nyamandhlovu area, Zimbabwe

The Nyamandhlovu aquifer is the main water resource in the semi-arid Umguza district in Matebeleland North Province in Zimbabwe. The rapid increase in water demand in the city of Bulawayo has prompted the need to quantify the available groundwater resources for sustainable utilization. Groundwater recharge estimation methods and results were compared: chloride mass balance method (19–62 mm/year); water-table fluctuation method (2–50 mm/year); Darcian flownet computations (16–28 mm/year); ¹⁴C age dating (22–25 mm/year); and groundwater modeling (11–26 mm/year). The flownet computational and modeling methods provided better estimates for aerial recharge than the other methods. Based on groundwater modeling, a final estimate for recharge (from precipitation) on the order of 15–20 mm/year is believed to be realistic, assuming that part of the recharge water transpires from the water table by deep-rooted vegetation. This recharge estimate (2.7–3.6% of the annual precipitation of 555 mm/year) compares well with the results of other researchers. The advantages/disadvantages of each recharge method in terms of ease of application, accuracy, and costs are discussed. The groundwater model was also used to quantify the total recharge of the Nyamandhlovu aquifer system (20?×?10⁶–25?×?10⁶ m³/year). Groundwater abstractions exceeding 17?×?10⁶ m³/year could cause ecological damage, affecting, for instance, the deep-rooted vegetation in the area.     

Geochemical constraints for the origin of thermal waters from western Turkey

The combined chemical composition, B and Sr isotopes, and the basic geologic setting of geothermal systems from the Menderes Massif in western Turkey have been investigated to evaluate the origin of the dissolved constituents and mechanisms of water–rock interaction. Four types of thermal water are present: (1) a Na–Cl of marine origin; (2) a Na–HCO₃ type with high CO₂ content that is associated with metamorphic rocks of the Menderes Massif; (3) a Na–SO₄ type that is also associated with metamorphic rocks of the Menderes Massif with H₂S addition; and (4) a Ca–Mg–HCO₃–SO₄ type that results from interactions with carbonate rocks at shallow depths. The Na–Cl waters are further subdivided based on Br/Cl ratios. Water from the Cumalı Seferihisar and Bodrum Karaada systems are deep circulated seawater (Br/Cl=sea water) whereas water from Çanakkale–Tuzla (Br/Cl<sea water) are from dissolution of Messinian evaporites. Good correlations between different dissolved salts and temperature indicate that the chemical composition of the thermal waters from non-marine geothermal systems is controlled by: (1) temperature dependent water–rock interactions; (2) intensification of reactions due to high dissolved CO₂ and possibly HCl gasses; and (3) mixing with overlying cold groundwater. All of the thermal water is enriched in B. The B isotopic composition (δ¹¹B=2.3‰ to 18.7‰; n=6) can indicate either leaching of B from the rocks, or B(OH)₃ degassing flux from deep sources. The large ranges in B concentrations in different rock types as well as in thermal waters from different systems suggest the water-rock mechanism. ⁸⁷Sr/⁸⁶Sr ratios of the thermal water are used to differentiate between solutes that have interacted with metamorphic rocks (⁸⁷Sr/⁸⁶Sr ratio as high as 0.719479) and carbonate rocks (low ⁸⁷Sr/⁸⁶Sr ratio of 0.707864).     

Pb-Pb age of sedimentary phosphorite reworking in Lower Riphean carbonate sediments,the Satka Formation of Southern Urals

The mineral composition and U-Pb and Rb-Sr systematics of phosphorites from the Satka Formation of Lower Riphean carbonates, the Burzyan Group of Southern Urals, are studied. Phosphorites occurring as small lenses between stromatolite layers are composed largely of fluorapatite with admixture of detrital quartz, feldspars, illite, and chlorite. Phosphorite samples have been subjected to stepwise dissolution in 1 N (fraction L-1) and 2 N (fraction L-2) HCl. As is established, the maximum apatite content is characteristic of fraction L-1, while fraction L-2 is enriched in products of dolomite and sulfide dissolution and in elements leached from siliciclastic components. The Sr content in the Satka apatites (280–560 ppm) is substantially lower as compared with that in unaltered marine apatite. The ⁸⁷Sr/⁸⁶Sr “initial ratio in the phosphorites studied (0.71705–0.72484) and host dolomites from the lower part of the Satka Formation is significantly higher than in the Early Riphean seawater that indicates a reset of the Rb-Sr original systems in sediments. The Pb-Pb age of 1340 ± 30 Ma (MSWD = 6.4) estimated based on 7 data points characterizing fractions L-1 and L-2 is younger than the formation time of overlying Burzyan sediments, being consistent, within the error range, with date of the Mashak rifting event recorded at the Early-Middle Riphean boundary. The comparative U-Pb characteristics of two soluble fractions (L-1 and L-2) and silicate residue of phosphorites show that epigenetic redistribution of Pb and U was characteristic of the phosphorite horizon only. The initial Pb isotope composition and μ (²³⁸U/²⁰⁴Pb) estimated according to model by Stacey and Kramers for the early diagenetic fluids in carbonate and phosphate sediments of the Satka Formation suggest that they were in isotopic equilibrium with erosion products of the Taratash crystalline complex.     

Uranium isotopes as a tracer of sources of dissolved solutes in the Han River,South Korea

The uranium (U) content and ²³⁴U/²³⁸U activity ratio were determined for water samples collected from Korea's Han River in spring, summer, and winter 2006 to provide data that might constrain the origin of U isotope fractionation in river water and the link between U isotope systematics in river waters and the lithological nature of the corresponding bedrock. The large difference in the major dissolved loads between the two major branches of the Han River, the North Han River (NHR) and South Han River (SHR), is reflected in the contrasting U content and ²³⁴U/²³⁸U activity ratio between the tributaries: low U content (0.08–0.75 nM; average, 0.34 nM) and small ²³⁴U/²³⁸U activity ratio (1.03–1.22; average, 1.09) in the NHR; and high U content (0.65–1.98 nM; average, 1.44 nM) and large ²³⁴U/²³⁸U activity ratio (1.05–1.45; average, 1.24) in the SHR. The large spatial differences in U content and ²³⁴U/²³⁸U activity ratio are closely related to both lithological differences between the two tributaries and groundwater input. The low U content and small ²³⁴U/²³⁸U activity ratio in the NHR arise mainly from a combination of surface and meteoric weathering of the dominant silicate rocks in this branch and congruent dissolution of already weathered (secular equilibrium) materials. In contrast, the high U content and large ²³⁴U/²³⁸U activity ratio in the SHR are ascribed to the dissolution of carbonates and black shales along with significant inputs of deep groundwater.     

Evaluating the impact of management scenarios and land use changes on annual surface runoff and sediment yield using the GeoWEPP: a case study from the Lighvanchai watershed,Iran

This study was undertaken to evaluate land use change impact and management scenarios on annual average surface runoff (SR) and sediment yield (SY) using the GeoWEPP tool in the Lighvanchai watershed (located in northwestern Iran). Following a sensitivity analysis, the WEPP model was calibrated (2005–2007) and validated (2008–2010) against monthly observed SY and SR. The coefficient of determination (R ²), Nash–Sutcliffe efficiency (NSE), mean bias error (MBE), and root-mean-square error (RMSE) were applied to quantitatively evaluate the WEPP model. The results indicate a satisfactory model performance with R ² > 0.80 and NSE > 0.60. Therefore, the model for current land use (scenario 1) was run for a 30-year time period (1982–2011). The annual average of SR and sediment load were predicted as 93,584 m³/year and 4340 ton/year, respectively. To reduce the annual average surface runoff and sediment yield at the watershed scale, the second scenario (alfalfa cultivation with suitable tillage) and the third scenario (grassland development) as two management scenarios of land use changes were defined by identifying the critical hillslopes. The rate of SR and sediment load in the second scenario were 42,096 m³/year and 429 ton/year, respectively. For the third scenario, the model predictions were 30,239 m³/year and 226 ton/year, respectively. Compared to the first scenario, the reduction rates in annual average of sediment load were about 90 and 94%, respectively. Moreover, for the second and third management scenarios, the reduction rates in annual average of SR were about 55 and 67%, respectively.     

Halogen signatures of biotites from the Maher-Abad porphyry copper deposit,Iran: characterization of volatiles in syn- to post-magmatic hydrothermal fluids

Copper and gold mineralization in the Maher-Abad area, eastern Iran, is closely related to multiple episodes of emplacement of a late Eocene granodiorite into a quartz-monzonitic stock and andesitic volcaniclastic rocks. Hypogene and supergene porphyry Cu–Au mineralization occurred within the porphyritic granodiorite and quartz-monzonite host rocks extensively altered into dominantly potassic, propylitic, phyllic, and argillic assemblages. Temperature and pressure estimates using the plagioclase–hornblende thermometer and Al-in-hornblende barometer indicate that the granodiorite intruded at 758 ± 10°C and 1.4 ± 0.2 kbar.

Biotites from the alteration zones have more variable Al^IV than those in the fresh granodiorite, but nearly all are close to the ideal phlogopite composition. Biotite compositions display an increase in Al₂O₃, FeO, TiO₂, and Cl, but a decrease in SiO₂ and F, from the porphyritic granodiorite and potassic to the transitional phyllic alteration zones. Biotite from the potassic zone (X _phl?=?0.63–0.67) possesses a moderate F content (0.53 to 0.82 wt.%) that is significantly higher than that in the phyllic zone (0.22 to 0.38 wt.%), exhibiting a positive correlation with X _Mg and negative correlation with Cl.

With a decrease in the temperature, log (fH₂O/fHF) and log (fH₂O/fHCl) values calculated for fluids equilibrated with biotite increase progressively from the granodiorite through the potassic to the phyllic zones, whereas log (fHF/fHCl) shifts towards more negative values. Fugacity ratio trends in the Maher-Abad porphyry copper deposit are quite similar to those of other porphyry copper systems. The decrease in halogen content of hydrothermal fluids towards outer parts of the deposits reflects an increase in the degree of mixing between magmatic fluid and meteoric water.     

Spatial patterns of the evolution of the chemical composition and discharge of river water in the Ob River basin

The discharge of major cations and dissolved organic carbon (C_org) with water of the Ob River and its tributaries along the natural zones within the Ob River basin was calculated, and the contribution of the underground component to the volumes of total discharge of the Ob River basin was estimated. It was demonstrated that the total chemical composition of river water and the geochemical discharge in the Ob River basin were consistent with the zoned hydroclimatic conditions controlling the character and duration of interaction in the water–rock system. It was established that the average ionic discharge of the Ob River increased from 6–7 × 10⁶ t/year near Barnaul to 46–47 × 10⁶ t/year near Salekhard; the discharge of dissolved C_org increased from 0.1 × 10⁶ to 3.8 × 10⁶ t/year. Multiple enrichment of underground waters of the Ob River in dissolved organic matter from the upper to the lower reaches was revealed.     

Geostatistical analysis of temporal and spatial variations in groundwater levels and quality in the Minqin oasis, Northwest China

Recognition of the temporal and spatial variations in groundwater levels and quality has become a prerequisite of formulating strategies for the sustainable development and utilization of water resources. In this study, data were obtained from 51 observation wells of depth to groundwater from 1999 to 2008 and 30 sampling wells of hydrochemical characteristics of groundwater in the Minqin oasis. The Kolomogorov–Semirnov test revealed that all data followed normal or log-normal distribution. A set of well-structured semivariograms also confirmed that the data had moderate (only for Mg²⁺ and K⁺) or strong spatial dependence. Based on spatial distribution, maps drawn using the ordinary Kriging interpolation method in different periods, the declining trend of the groundwater table was found to have been relieved since 2007, with the mean water table dropping 4.65 m from 1999 to 2008. Spatial comparison results further showed that the variations in groundwater levels in Baqu and Quanshan were more evident than those in Huqu, with mean decline rates of 0.64, 0.93, and 0.41 m/year, respectively. The mean value of total dissolved solids (TDS) was 3.34 g/L, and the groundwater in 76.2 % of the study area was brackish (TDS ≥ 1.0 g/L). From south to north, the groundwater types can be classified into three obvious zones based on the major ion distributions: SO₄ ^2?–HCO₃ ^?–Na⁺–Ca²⁺ type in Baqu, SO₄ ^2?–Na⁺–Ca²⁺ type in Quanshan, and SO₄ ^2?–C1^?–Na⁺ type in Huqu. TDS increased from the 1970 to 2005 and gradually decreased thereafter.     

Petrological and Os Isotopic Characteristics of Zedong Peridotites in the Eastern Yarlung–Zangbo Suture in Tibet

The Zedong ophiolites in the eastern Yarlung–Zangbo suture zone of Tibet represent a mantle slice of more than 45 km~2. This massif consists mainly of mantle peridotites, with lesser gabbros, diabases and volcanic rocks. The mantle peridotites are mostly harzburgite, lherzolite; a few dike-like bodies of dunite are also present. Mineral structures show that the peridotites experienced plastic deformation and partial melting. Olivine(Fo89.7–91.2), orthopyroxene(En_(88–92)), clinopyroxene(En_(45–49) Wo_(47–51) Fs_(2–4)) and spinel [Mg~#=100×Mg/(Mg+Fe)]=49.1–70.7; Cr~#=(100×Cr/(Cr+Al)=18.8–76.5] are the major minerals. The degree of partial melting of mantle peridotites is 10%–40%, indicating that the Zedong mantle peridotites may experience a multi–stage process. The peridotites are characterized by depleted major element compositions and low REE content(0.08–0.62 ppm). Their "spoon–shaped" primitive–mantle normalized REE patterns with(La/Sm)_N being 0.50–6.00 indicate that the Zedong ultramafic rocks belong to depleted residual mantle rocks. The PGE content of Zedong peridotites(18.19–50.74 ppb) is similar with primary mantle with Pd/Ir being 0.54–0.60 and Pt/Pd being 1.09–1.66. The Zedong peridotites have variable, unradiogenic Os isotopic compositions with ~(187)Os/~(188)Os=0.1228 to 0.1282. A corollary to this interpretation is that the convecting upper mantle is heterogeneous in Os isotopes. All data of the Zedong peridotites suggest that they formed originally at a mid-ocean ridge(MOR) and were later modified in supra–subduction zone(SSZ) environment.     

An experimental determination of chlorine isotope fractionation in acid systems and applications to volcanic fumaroles

The δ³⁷Cl values of volcanic fumarole gases and bubbling springs were measured from the Central American and the Kurile arcs. Low temperature gas samples from the Central American arc have δ³⁷Cl values generally between −2 and 2‰, whereas high-temperature fumaroles (>100 °C) range from 4 to 12‰, with several outliers. This is in contrast to the high-temperature fumaroles from the Kurile island Kudryavy which have slightly positive δ³⁷Cl values, averaging 0.8‰ (±0.6, 1σ), and from our previous work on Izu and Mariana arc samples in which the δ³⁷Cl values of fumarole and ash samples are similar to each other and negative. Assuming that the source for the high-T Central American fumaroles has typical subduction δ³⁷Cl values (−2.5 to 1‰), then there must be a large Cl isotope fractionation in the near-surface fumarolic system. The most likely fractionation mechanism for the high δ³⁷Cl values is between Cl⁻_aq − HCl(g), but published theoretical fractionation for this pair is only ∼1.5‰, insufficient to explain the large range of values observed in the fumaroles. Three experiments were undertaken in order to identify a process that could cause the wide range of δ³⁷Cl values observed in the high-temperature fumaroles. Results are the following: (1) A sub-boiling equilibration experiment between aqueous chloride and HCl gas had , in agreement with the theoretical calculations. (2) Evaporation of HCl(g) from hydrochloric acid at room temperature had fractionation in the opposite sense, with a . (3) A ‘synthetic fumarole’ gave large positive fractionations up to 9‰, with ³⁷Cl strongly partitioned into the vapor phase. The ‘fumarole’ experiments were made by bubbling dry air through boiling hydrochloric acid in an Erlenmeyer flask, and collecting the evolved HCl(g) in a second ‘downstream’ flask filled with distilled water. This extreme enrichment is likely due to a distillation process in which ³⁷Cl-enriched HCl(g) is stripped from the hydrochloric acid followed by a significant fraction of the light HCl(g) redissolving into the constantly condensing water vapor on the walls of the first flask. This distillation experiment creates a Cl isotope fractionation that is the same order of magnitude as observed in the high-temperature fumaroles in Central America. These results suggest that there must be a H₂O liquid-vapor region in the sub-surface fumarole conduit where light Cl is stripped from the HCl gas as it passes through the fumarole. Similar ³⁷Cl enrichments are expected in fossil epithermal boiling systems.     

Early‐Cretaceous Syenites and Granites in the Northeastern Tengchong Block,SW China: Petrogenesis and Tectonic Implications

Whole-rock major and trace element and Sr-Nd isotopic data, together with zircon LA ICPMS in-situ U-Pb and Hf isotopic data of the syenites and granites in the Tengchong Block are reported in order to understand their petrogenesis and tectonic implications. Zircon U-Pb data gives the emplacement ages of ca. 115.3±0.9 Ma for syenites and 115.7±0.8 Ma for granites, respectively. The syenites are characterized by low SiO_2 content(62.01–63.03 wt%) and notably high Na_2O content(7.04–7.24 wt%) and Na_2O/K_2O ratios(2.02–2.10), low MgO, Fe_2O_3 T and TiO_2, enrichment of LILEs(large-ion lithophile element) such as Rb, Th, U, K, and Pb) and obvious depletion HFSE(high field strength element; e.g. Nb, Ta, P, and Ti) with clearly negative Eu anomalies(d Eu=0.53–0.56). They also display significant negative whole-rock εNd(t) values of-6.8 and zircon εHf(t) values(-9.11 to-0.27, but one is +5.30) and high initial ~(87) Sr/~(86) Sr=0.713013. Based on the data obtained in this study, we suggest that the ca. 115.3 Ma syenites were possibly derived from a sodium-rich continental crustal source, and the fractionation of some ferro-magnesian mineral and plagioclase might occur during the evolution of magma. The granites have high SiO_2 content(71.35–74.47 wt%), metaluminous to peraluminous, low Rb/Ba, Rb/Sr, and Al_2O_3/(MgO+FeOT+TiO_2) ratios and moderate(Al_2O_3+MgO+FeOT+TiO_2) content. They show low initial ~(87) Sr/~(86) Sr(0.703408 to 0.704241) and εNd(t) values(-3.8 to-3.5), plotted into the evolutionary trend between basalts and lower crust. Hence, we suggest that the granites were derived from the melting of mixing sources in the ancient continental crust involving some metabasaltic materials and predominated metasedimentary greywackes. Together with data in the literatures, we infer that the Early Cretaceous magmatism in the Tengchong block was dominated by magmas generated by the partial melting of ancient crustal material, which represent the products that associated to the closure of Bangong-Nujiang Meso-Tethys.     

Environmental isotopic and hydrochemical study of water in the karst aquifer and submarine springs of the Syrian coast

The groundwater of major karst systems and submarine springs in the coastal limestone aquifer of Syria has been investigated using chemical and isotopic techniques. The δ¹⁸O values of groundwater range from ?6.8 to ?5.05‰, while those for submarine springs vary from ?6.34 to +1.08‰ (eastern Mediterranean seawater samples have a mean of +1.7‰). Groundwater originates from the direct infiltration of atmospheric water. Stable isotopes show that the elevation of the recharge zones feeding the Banyas area (400–600 m a.s.l.) is higher than that feeding the Amrit area (100–300 m a.s.l.). The ¹⁸O_extracted (¹⁸O content of the seawater contribution) for the major submarine springs suggests a mean recharge area elevation of 600–700 m a.s.l., and lower than 400 m a.s.l. for the spring close to Amrit. Based on the measured velocity and the percentage of fresh water at the submarine springs outlet, the estimated discharge rate is 350 million m³/year. The tritium concentrations in groundwater (1.6–5.9 TU) are low and very close to the current rainfall values (2.9–5.6 TU). Adopting a model with exponential time distribution, the mean turnover time of groundwater in the Al-sen spring was evaluated to be 60 years. A value of about 3.7 billion m³ was obtained for the maximum groundwater reservoir size.     

江西阳储岭两期岩浆活动与钨成矿作用的关系：来自黑云母地球化学的证据

阳储岭斑岩型W-Mo矿床位于江南造山带中部,是华南地区最早发现的斑岩型钨钼矿床。已探明WO₃资源储量6.13万吨(平均品位0.2%),Mo资源储量1.69万吨(平均品位0.03%～0.06%),其成矿作用与中生代花岗质岩浆活动密切相关。区内发育早期花岗闪长岩和晚期二长花岗斑岩,钨矿体以细脉状和浸染状产于二长花岗斑岩体内,而花岗闪长岩内未见矿化。两期岩浆活动与钨成矿的关系尚不明确,制约其含矿差异性的因素尚不清楚。本文以花岗闪长岩和二长花岗斑岩中的黑云母为研究对象,对比研究两类岩浆结晶分异程度、氧逸度、岩浆流体卤素浓度,探讨其对钨成矿的制约。黑云母主量元素分析结果显示,阳储岭两类岩浆岩均为壳源,但显著不同于S型花岗岩的Mg/(Fe+Mg)和Al^VI值,指示其具有I型花岗岩的特征。黑云母的微量元素信息显示,相对于花岗闪长岩中的黑云母(类型一),二长花岗斑岩中的黑云母(类型二)显示低的K/Rb、Nb/Ta比值,高的Rb、Cs、Nb和Ta含量,表明其分异程度较花岗闪长岩更高,更有利于钨的富集。两类黑云母所指示的岩浆氧逸度均在NNO缓冲线附近,表明其母岩...     

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

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

Preliminary isotopic studies in the Bida basin,central Nigeria

The area of the Bida basin is lacking in essential data for effective groundwater management. Hydrological studies using environmental isotopes (²H,³H,¹³C,¹⁸O) were carried out in the basin during the 1987–1988 hydrological year on samples of rainfall, streams, springs, and groundwater. The results obtained results do not indicate the presence of paleowaters; rather all groundwaters in the basin are found to be of meteoric origin as bothD and ¹⁸O values of the samples, plotted in the conventional way, align with the meteoric water line (MWL). Moreover, these data show the deeper, and apparently older, groundwater to be more depleted in the heavy stable isotopes than the shallower, relatively younger groundwaters, indicating recharge under cooler climatic conditions for the former. Measured tritium values range from 0.7 to 23.8 TU and show a variation with both depth and lithology, while at the same time indicating that active recent recharge is taking place basin-wide. The few¹³C data available were used to illustrate the effect of pumping on the carbonate geochemistry of the groundwaters. Also, the stable isotope data from the basin were compared with similar data from other parts of the country to show the continental effect.     

The ion-pair constant and other thermodynamic properties of HCl up to 350°C

Solubilities of silver chloride in aqueous hydrochloric acid solutions have been determined from 100 up to 350°C. From these measurements, the ionisation constant of HC1 has been evaluated up to 225°C. Evidence is presented to show that a protonated silver species, HAgCl₂⁰, exists at 275°C and above. Available experimental data up to 200°C have been firted to Pitzer's equation to generate an algorithm to calculate stoichiometric activity and osmotic coefficients of HCl up to 350°C and concentrations up to at least 3.0 m. Using the present results and those of Wrightet al. (1961), Pearsonet al. (1963) and Lukashowet al. (1976), the dissociation constant (K_d) of HCl as a function of temperature is described by the equation log₁₀K = 2136.898 + 1.020349T−4.5045 × 10⁻⁴T²−50396.40/T−901.770 10g₁₀T (Tin °K) which is valid in the range 25–350°C. Calculated enthalpy (ΔH⁰), entropy (ΔS⁰) and heat capacity change (ΔC_p⁰) functions for HCl dissociation have been rationalized in terms of changing solute and solvent characteristics as temperature is raised.     

SIMS Bias on Isotope Ratios in Ca‐Mg‐Fe Carbonates (Part III): δ18O and δ13C Matrix Effects Along the Magnesite–Siderite Solid‐Solution Series

This study explores the effects of cation composition on mass bias (i.e., the matrix effect), which is a major component of instrumental mass fractionation (IMF) in the microanalyses of δ¹³C and δ¹⁸O by SIMS in carbonates of the magnesite–siderite solid‐solution series (MgCO₃–FeCO₃). A suite of twelve calibration reference materials (RMs) was developed and documented (calibrated range: Fe# = 0.002–0.997, where Fe# = molar Fe/[Mg + Fe]), along with empirical expressions for regressing calibration data (affording residuals < 0.5‰ relative to certified reference material NIST‐19). The calibration curves of both isotope systems are non‐linear and have, over a 2‐year period, fallen into one of two distinct but largely self‐consistent shape categories (data from ten measurement sessions), despite adherence to well‐established analytical protocols for carbonate δ¹³C and δ¹⁸O analyses at WiscSIMS (CAMECA IMS 1280). Mass bias was consistently most sensitive to changes in composition near the magnesite end‐member (Fe# 0–0.2), deviating by up to 4.5‰ (δ¹³C) and 14‰ (δ¹⁸O) with increasing Fe content. The cause of variability in calibration curve shapes is not well understood at present and demonstrates the importance of having available a sufficient number of well‐characterised RMs so that potential complexities of curvature can be adequately delineated and accounted for on a session‐by‐session basis.     

Noble Gas and Stable Isotopic Constraints on the Origin of the Ag–Cu Polymetallic Ore Deposits in the Baiyangping Area,Yunnan Province,SW China

The Lanping basin, Yunnan province, SW China, is located at the juncture of the Eurasian and Indian Plates in the eastern part of the Tibetan Plateau. The Lanping basin, in the Sanjiang Tethyan metallogenic province, is a significant Cu–Ag–Zn–Pb mineralized belt in China that includes the largest sandstone‐hosted Zn–Pb deposit in the world, the Jinding deposit, as well as several Ag–Cu deposits (the Baiyangping and Jinman deposits). These deposits, with total reserves of over 16.0 Mt Pb + Zn, 0.6 Mt Cu, and 7,000 t Ag, are mainly hosted in Meso‐Cenozoic clastic rocks and are dominantly controlled by two Cenozoic thrust systems developed in the western and eastern segments of the basin. The Baiyangping, Babaoshan, and Hetaoqing ore deposits are representative of the epithermal base metal deposits in the Lanping basin. The microthermometric data show that the ore‐forming fluids for these deposits were low temperature (110–180 °C) and had bimodal distribution of salinity at moderate and mid to high salinities (approximately 2–8 wt.% and 18–26 wt.% NaCl equivalent). The C and O isotope data indicate that the ore‐forming fluids were related to hot basin brines. We present new He and Ar isotope data on volatiles released from fluid inclusions contained in sulfides and in barite in these three deposits. ³He/⁴He ratios of the ore‐forming fluids are 0.01 to 0.14 R/Ra with a mean of 0.07 Ra (where R is the ³He/⁴He ratio and Ra is the ratio for atmospheric helium). This mean value is intermediate to typical ³He/⁴He ratios for the crust (R/Ra = 0.01 to 0.05) and the ratio for air‐saturated water (R/Ra = 1). The mean ratio is also significantly lower than the ratios found for mantle‐derived fluids (R/Ra = 6 to 9). The ⁴⁰Ar/³⁶Ar ratios of the ore‐forming fluids range from 298 to 382 with a mean of 323. This value is slightly higher than that for the air‐saturated water (295.5). The ³He/⁴He ratios of fluids from the fluid inclusions imply that the ore‐forming fluid for the Baiyangping, Babaoshan, and Hetaoqing deposits was derived from the crust and that any mantle‐derived He was negligible. The content of the radiogenic Ar ranges between 0.2 to 20.4%, and the proportion of air‐derived ⁴⁰Ar averages 94.1%. This indicates that atmospheric Ar was important in the formation of these deposits but that some radiogenic ⁴⁰Ar was derived from crustal rocks. Based on these observations coupled with other geochemical evidence, we suggest that the ore‐forming fluids responsible for the formation of the Ag–Cu–Pb–Zn polymetallic ore deposits in the Baiyangping area of the Lanping basin were mainly derived from crustal fluids. The fluids may have mixed with some amount of air‐saturated water, but there was no significant involvement of mantle‐derived fluids.