Hydrochemistry of Salt Lakes of the Qinghai-Tibet Plateau, China

The authors have carried out scientific investigations of salt lakes on the Qinghai-Tibet Plateau since 1956 and collected 550 hydrochemical data from various types of salt lakes. On that basis, combined with the tectonic characteristics of the plateau, the hydrochemical characteristics of the salt lakes of the plateau are discussed. The salinity of the lakes of the plateau is closely related to the natural environment of lake evolution, especially the climatic conditions. According to the available data and interpretation of satellite images, the salinity of the lakes of the plateau has a general trend of decreasing from north and northwest to south and southeast, broadly showing synchronous variations with the annual precipitation and aridity (annual evaporation/annual precipitation) of the modern plateau. The pH values of the plateau salt lakes are related to both hydrochemical types and salinities of the lake waters, i.e., the pH values tend to decrease from the carbonate type → sodium sulfate subtype → magnesium sulfate subtype → chloride type; on the other hand, a negative correlation is observed between the pH and salinities of the lakes. Geoscientists and biological limnologists generally use main ions in salt lakes as the basis for the hydrochemical classification of salt lakes. The common ions in salt lakes are Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^? SO₄ ^2?, CO₃ ^2?, and HCO₃ ^?. In this paper, the Kurnakov-Valyashko classification is used to divide the salt lakes into the chloride type, magnesium sulfate subtype, sodium sulfate subtype and carbonate type, and then according to different total alkalinities (K _C = Na₂CO₃ + NaHCO₃/total salt × 100%) and different saline mineral assemblages, the carbonate type is further divided into three subtypes, namely, strong carbonate subtype, moderate carbonate subtype and weak carbonate subtypes. According to the aforesaid hydrochemical classifications, a complete and meticulous hydrochemical classification of the salt lakes of the plateau has been made and then a clear understanding of the characteristics of N–S hydrochemical zoning and E-W hydrochemical differentiation has been obtained. The plateau is divided into four zones and one area. There is a genetic association between certain saline minerals and specific salt lake hydrochemical types: the representative mineral assemblages of the carbonate type of salt lake is borax (tincalconite) and borax-zabuyelite (L₂CO₃) and alkali carbonate-mirabilite; the representative mineral assemblages of the sodium sulfate subtype are mirabilite (thenardite)-halite and magnesium borate (kurnakovite, inderite etc.)-ulexite-mirabilite; the representative mineral assemblages of the magnesium sulfate subtype are magnesium sulfate (epsomite, bloedite)-halite, magnesium borate-mirabilite, and mirabilite-schoenite-halite, as well as large amount of gypsum; The representative mineral assemblages of the chloride type are carnallite-bischofite-halite and carnallite-halite, with antarcticite in a few individual salt lakes. The above-mentioned salt lake mineral assemblages of various types on the plateau have features of cold-phase assemblages. Mirabilite and its associated cold-phase saline minerals are important indicators for the study of paleoclimate changes of the plateau. A total of 59 elements have been detected in lake waters of the plateau now, of which the concentrations of Na, K, Mg, Ca, and Cl, and SO₄ ^2?, CO₃ ^2?, and HCO₃ ^? ions are highest, but, compared with the hydrochemical compositions of other salt lake regions, the plateau salt lakes, especially those in the southern Qiangtang carbonate type subzone (I₂), contain high concentrations of Li, B, K, Cs, and Rb, and there are also As, U, Th, Br, Sr, and Nd positive anomalies in some lakes. In the plateau lake waters, B is intimately associated with Li, Cs, K and Rb and its concentration shows a general positive correlation with increasing salinity of the lake waters. The highest positive anomalies of B, Li, Cs, and K center on the Ngangla Ringco Lake area in the western segment of the southern Qiangtang carbonate type subzone (I₂) and coincide with Miocene volcanic-sedimentary rocks and high-value areas of B, Li, and Cs of the plateau. This strongly demonstrates that special elements such as B, Li, and Cs on the plateau were related to deep sources. Based on recent voluminous geophysical study and geochemical study of volcanic rocks, their origin had close genetic relation to anatectic magmatism resulting from India–Eurasia continent–continent collision, and B–Li (-Ce) salt lakes in the Cordillera Plateau of South America just originated on active continental margins, both of which indicate that global specific tectonically active belts are the main cause for the high abundances of B, Li, and Cs (K and Rb) in natural water and mineralization of these elements.     

Salinity control on long-chain alkenone distributions in lake surface waters and sediments of the northern Qinghai-Tibetan Plateau, China

Long-chain alkenones in lacustrine settings are potentially excellent biomarkers for the reconstruction of past terrestrial environmental conditions, and have been found in many different types of lakes around the globe. A wider range of factors influence the occurrence and distribution of alkenones in lake sediments and waters when compared to marine systems. Lake environmental conditions, such as temperature (in particular) and salinity, are among the key factors controlling alkenone distributions in lacustrine settings. Here we investigated alkenone distribution patterns in lakes of the northern Qinghai-Tibetan Plateau, China, and their possible relationship with environmental conditions, by analyzing paired samples of suspended particulate matter in surface waters and surface sediments. Salinity of investigated lake waters ranges from almost 0 to ∼100 g/L, while temperature variation among the lakes is minimal, effectively eliminating temperature effects on the alkenone distribution patterns observed here. We show that (1) alkenone concentrations vary substantially between the lakes, yet controlling mechanisms remain elusive; (2) C₃₇/C₃₈ ratios are substantially lower in the lakes of the Qaidam Basin than in the Lake Qinghai region, probably indicating different alkenone producers in the two regions; and (3) large variations in %C_37:4 (the percentage of the C_37:4 alkenone), determined from both surface waters and sediments, are negatively correlated with salinity. We suggest that the %C_37:4 index could be used as a salinity indicator at least on a regional scale, with careful considerations of other potentially complicating factors. However, potential reasons for why salinity could significantly affect %C_37:4 values need further investigation.     

Application of hydrogeochemistry to uranium exploration in the pine creek geosyncline, northern territory, Australia

In the Pine Creek Geosyncline, fast moving, annually recharged, low-salinity ground waters dissolve uranium- and magnesium-enriched gangue minerals from mineralized aquifer rocks. The level of dissolved uranium depends on prevailing pH, Eh, salinity and degree of adsorption, which limits its effectiveness as an exploration indicator. Near each known deposit, leaching of magnesium-enriched gangue minerals produces ground waters with very similar major-element concentration plots, the shape of which constitutes a mineralized aquifer “signature”. Gangue minerals also supply high levels of Mg²⁺ (expressed as NMg = [Mg²⁺]/[Ca²⁺ + Mg²⁺ + Na⁺ + K⁺] in milliequivalents per litre) to contained ground waters, NMg > 0.8 being common in ground waters from mineralized aquifers at each Pine Creek Geosyncline deposit. Data from Ranger One No. 3 ore body illustrates how progressive mixing of waters from mineralized and unmineralized aquifers causes graded reductions in NMg, which, when plotted onto a ground plan, delineate a hydrogeochemical aureole.High NMg (> 0.8) coincides with high uranium concentration (> 20 μg/l of U) in ground waters near Nabarlek and Ranger. Because pH-Eh conditions in aquifers at Jabiluka depress uranium solution, < 10 μg/l of U is present, although NMg values are generally > 0.8. To date NMg has always been < 0.8 in nonmineralized aquifer waters, whereas uranium may be > 50 μg/l in ground waters from felsic igneous aquifers, which can be identified as uneconomic by low (< 0.4) NMg, and by a fixed relationship between uranium and co-leached species such as F^- and soluble salts.Measurements of pH, Eh, salinity, Fe(II), Ca, Mg, Na, K, Cl, SO₄, total carbonate, phosphate, F^-, Cu, Pb, Zn and U in waters from 48 percussion holes in and near the Koongarra ore bodies have been related to mineralogy recorded in drill logs. The composition of waters from 20 holes near and along strike from known mineralization, fitted the mineralized aquifer “signature”, had NMg > 0.8 and uranium up to 4100 μ/l. These data confirm the use in this region of NMg as a hydrogeochemical indicator of uranium mineralization; they also indicate additional zones of possible mineralization.     

The origin of high bicarbonate and fluoride concentrations in waters of the Main Ethiopian Rift Valley, East African Rift system

Thermal waters in the Main Ethiopian Rift Valley are characterized by high Na, bicarbonate and fluoride concentrations, and near-neutral to alkaline pH. Sodium, bicarbonate and fluoride are positively correlated in the waters. The principal reason for the bicarbonate in the area is the high rate of carbon dioxide outgassing. This, combined with acid volcanics, geothermal heating, low Ca and low salinity, is also one of the causes of high fluoride in this part of the active volcanic zone of the East African Rift. Evaporative concentration is responsible for the high salinity, alkalinity and fluoride in the closed-basin lakes of the region. The waters are undersaturated with respect to fluoride and anhydrite. Calcium tends to be fixed in Ca bearing minerals such as calcite and epidote, which are abundant in the system. Hence, it appears that fluoride is a mobile component in acid volcanic geothermal systems.     

Behavior of Uranium in the Yellow River Plume (Yellow River Estuary)

The Yellow River (Huanghe) is the second largest river in China and is known for its high turbidity. It also has remarkably high levels of dissolved uranium (U) concentrations (up to 38 nmol 1^-1). To examine the mixing behavior of dissolved U between river water and seawater, surface water samples were collected along a salinity gradient from the Yellow River plume during September 2004 and were measured for dissolved U concentration,²³⁴U:²³⁸U activity ratio, phosphate (PO₄ ^3–), and suspended particulate matter. Laboratory experiments were also conducted to simulate the mixing process in the Yellow River plume using unfiltered Yellow River water and filtered seawater. The results showed a nonconservative behavior for dissolved U at salinities < 20 with an addition of U to the plume waters estimated at about 1.4 X 10⁵ mol yr^–1. A similarity between variations in dissolved U and PO₄ ^3– with salinity was also found. There are two major mechanisms, desorption from suspended sediments and diffusion from interstitial waters of bottom sediments, that may cause the elevated concentrations of dissolved U and PO₄ ^3– in mid-salinity waters. Mixing experiments indicate that desorption seems more responsible for the elevated dissolved U concentrations, whereas diffusion influences more the enrichment of PO₄ ^3–.     

Features of acid–saline systems of Southern Australia

The discovery of layered, SO₄-rich sediments on the Meridiani Planum on Mars has focused attention on understanding the formation of acid–saline lakes. Many salt lakes have formed in southern Australia where regional groundwaters are characterized by acidity and high salinity and show features that might be expected in the Meridiani sediments. Many (but not all) of the acid–saline Australian groundwaters are found where underlying Tertiary sediments are sulfide-rich. When waters from the formations come to the surface or interact with oxidised meteoric water, acid groundwaters result. In this paper examples of such waters around Lake Tyrrell, Victoria, and Lake Dey-Dey, South Australia, are reviewed. The acid–saline groundwaters typically have dissolved solids of 30–60 g/L and pH commonly <4.5. Many contain high concentrations of Fe and other metals, leached from local sediments. The combination of acidity and salinity also releases Ra. Around salt-lakes, these acidic waters often emerge at the surface in marginal spring zones where the low density (ρ ∼ 1.04) regional water flows out over the denser (ρ ∼ 1.16) lake brines. In the spring zones examined, large amounts of Fe are commonly precipitated. In a few places minerals of the alunite-jarosite family are formed which can trap many other metals, including Ra. The studied groundwater systems were discovered by U exploration programs following up radiometric anomalies related to this Ra. Evaporation concentrates the lesser soluble salts (gypsum and some halite) on the surface of the lakes. The lake brines contain most of the more soluble salts and form a column within the porous sediments which is held in place by hydrostatic forces around the salt-lake. These brines are near-neutral in pH.     

The evolution of alkaline, saline ground- and surface waters in the southern Siberian steppes

Groundwaters, river and lake waters have been sampled from the semi-arid Siberian Republic of Khakassia. Despite the relatively sparse data set, from a diversity of hydrological environments, clear salinity-related trends emerge that indicate the main hydrochemical evolutionary processes active in the region. Furthermore, the major ion chemistry of the evolution of groundwater baseflow, via rivers, to terminal saline lake water, can be adequately and simply modelled (using PHREEQCI) by invoking: (i) degassing of CO₂ from groundwater as it emerges as baseflow in rivers (rise in pH); (ii) progressive evapoconcentration of waters (parallel accumulation of Cl⁻, Na⁺, SO₄²⁻, and increase in pH due to common ion effect); and (iii) precipitation of calcite (depletion of Ca from waters, reduced rate of accumulation of alkalinity). Dolomite precipitation is ineffective at constraining Mg accumulation, due to kinetic factors. Silica saturation appears to control dissolved Si in low salinity waters and groundwaters, while sepiolite saturation and precipitation depletes Si from the more saline surface waters. Gypsum and sodium sulphate saturation are only approached in the most saline environments. Halite remains unsaturated in all waters. Sulphate reduction processes are important in the lower part of lakes.     

The Equation of State of Lakes

In recent years, a number of workers have studied the stability of deep lakes such as Lake Tanganyika, Lake Baikal and Lake Malawi. In this paper, the methods that can be used to determine the effect that the components of lakes have on the equation of state are examined. The PVT properties of Lakes have been determined by using apparent molal volume data for the major ionic components of the lake. The estimated PVT properties (densities, expansibility and compressibilities) of the lakes are found to be in good agreement with the PVT properties (P) of seawater diluted to the same salinity. This is similar to earlier work that showed that the PVT properties of rivers and estuarine waters could also be estimated from the properties of seawater.The measured densities of Lake Tanganyika were found to be in good agreement (± 2 × 10^-6 g cm^-3) with the values estimated from partial molal properties and the values of seawater at the same total salinity (S_T = 0.568). The increase in the densities of Lake Tanganyika waters increased due to changes in the composition of the waters. The measured increase in the measured density (45 × 10^-6 g cm^-3) is in good agreement (46 × 10^-6 g cm^-3) with the values calculated for the increase in Na⁺, HCO₃ ^-, Mg²⁺, Ca²⁺ and Si(OH)₄.Methods are described that can be used to determine the conductivity salinity of lakes using the equations developed for seawater. By combining these relationships with apparent molal volume data, one can relate the PVT properties of the lake to those of seawater.     

Aquatic geochemistry of small lakes: Effects of environment changes

This paper reports the results of an extensive investigation of water chemistry in the small lakes of European Russia and Western Siberia along a climatic gradient. It was demonstrated that small lakes unaffected by any direct contamination can be used as indicators of natural geochemical conditions of water formation, as well as global and regional fluxes of airborne pollution and climate warming. A novel concept was developed for within- and between-zone variability in water chemistry over vast areas of tundra, taiga, forest, and steppe, and contributions of natural and anthropogenic factors to its formation under present-day conditions were estimated. A proposed predictive scenario showed that climate warming will result in an increase in water salinity in southern regions and ubiquitous phosphorus enrichment in terrestrial waters; the hydrologic and geochemical conditions of water formation in northern Siberia will change significantly in response to permafrost thawing. Zonal features in the development of anthropogenically-induced processes in terrestrial surface waters (acidification, eutrophication, and metal enrichment) were determined. It was demonstrated that, in addition to naturally acidified lakes with high contents of humic acids, acid lakes of anthropogenic origin occur over the whole humid region discussed here, and acidification processes were characterized for each subregion. The trophic status of lakes and limitation of their bioproductivity with respect to nutrients were estimated. The concentrations and distribution of trace elements were analyzed in terrestrial waters from various climatic zones of European Russia and Western Siberia, and the first estimates were obtained for the mean concentrations and coefficients of migration of a wide range of elements in terrestrial freshwaters. We distinguished a group of metal (Mo, As, U, Bi, Sb, Cd, Ag, Se, Re, Pb, Cd, W, etc.) the enrichment of which in natural waters results from their global dispersion in the environment. Experimental results and natural observations are presented on the processes of metal ion complexation with humus substances, and sequences of their increasing activity in competing for organic ligands were derived. Data are presented on the speciation of metals depending on natural water chemistry in the tundra, taiga, and steppe zones. The pioneering investigations on the geochemistry of natural waters allowed us to substantiate new regional norms for water quality.     

The regularities of distribution of radionuclides and reare-earth elements in bottom sediments of Siberian lakes

Geochemical studies of the ecosystems of 184 Siberian lakes in three largest zones of northern Asia (humid, arid, and semiarid) and in mountainous area were carried out. The contents of natural radionuclides, radiocesium, and rare-earth elements in conjugate components of the systems and the types of the main sources of the bottom sediment material have been determined.Dating of the bottom sediments was made by the activity of radioisotopes ¹³⁷Cs and ²¹⁰Pb, which permitted estimation of the sedimentation rates in lakes in different regions of Siberia: 0.35 cm/year in the south and 0.25–0.3 cm/year in the north.Six main ions have been determined in the waters of the studied lakes: Ca²⁺, Mg²⁺, Na⁺, HCO₃^?, SO₄^2?, and Cl^?. The distribution of natural radionuclides in the stratified sections of bottom sediments of Siberian lakes evidences the stable sedimentation and characterizes their contents in the soils of water-catchment areas, which can be considered background contents there. Sediments enriched in organic matter have higher concentrations of U and lower ones of Th and K. The Th/K ratio in the studied bottom sediments is the same as in the soils. The Th/U ratios are somewhat lower than those in the soils because U is accumulated by chemogenic and organic components. The overall ¹³⁷Cs pollution of bottom sediments of Siberian lakes is close to the global background (40 mCi /km² in 2000), but in the Altai Territory and Buryatia and Altai Republics it is twice higher. The uneven areal and temporal distribution of residual radiocesium is observed not only in the lacustrine sediments but also in the lake water areas. The REE patterns of bottom sediments of different mineral types are similar to those of continental crust and clays of the Russian Platform, though organogenic and carbonate sediments have higher absolute REE contents than terrigenous ones. Pelitic fraction is the main REE concentrator in the bottom sediments.     

Salinity reflux and dolomitization of southern Australian slope sediments: the importance of low carbonate saturation levels

Anomalously saline waters in Ocean Drilling Program Holes 1127, 1129, 1130, 1131 and 1132, which penetrate southern Australian slope sediments, and isotopic analyses of large benthic foraminifera from southern Australian continental shelf sediments, indicate that Pleistocene–Holocene meso‐haline salinity reflux is occurring along the southern Australian margin. Ongoing dolomite formation is observed in slope sediments associated with marine waters commonly exceeding 50‰ salinity. A well‐flushed zone at the top of all holes contains pore waters with normal marine trace element contents, alkalinities and pH values. Dolomite precipitation occurs directly below the well‐flushed zone in two phases. Phase 1 is a nucleation stage associated with waters of relatively low pH (ca 7) caused by oxidation of H₂S diffusing upward from below. This dolomite precipitates in sediments < 80 m below the sea floor and has δ¹³C values consistent with having formed from normal sea water (? 1‰ to + 1‰ Vienna Pee Dee Belemnite). The Sr content of Phase 1 dolomite indicates that precipitation can occur prior to substantial metastable carbonate dissolution (< 300 ppm in Holes 1129 and 1127). Dolomite nucleation is interpreted to occur because the system is undersaturated with respect to the less stable minerals aragonite and Mg‐calcite, which form more readily in normal ocean water. Phase 2 is a growth stage associated with the dissolution of metastable carbonate in the acidified sea water. Analysis of large dolomite rhombs demonstrates that at depths > 80 m below the sea floor, Phase 2 dolomite grows on dolomite cores precipitated during Phase 1. Phase 2 dolomite has δ¹³C values similar to those of the surrounding bulk carbonate and high Sr values relative to Phase 1 dolomite, consistent with having formed in waters affected by aragonite and calcite dissolution. The nucleation stage in this model (Phase 1) challenges the more commonly accepted paradigm that inhibition of dolomitization by sea water is overcome by effectively increasing the saturation state of dolomite in sea water.     

Formation and stability of schwertmannite in acidic mining lakes

Schwertmannite (ideal formula: Fe₈O₈(OH)₆SO₄) is typically found as a secondary iron mineral in pyrite oxidizing environments. In this study, geochemical constraints upon its formation are established and its role in the geochemical cycling of iron between reducing and oxidizing conditions are discussed. The composition of surface waters was analyzed and sediments characterized by X-ray diffraction, FTIR spectroscopy and determination of the Fe:S ratio in the oxalate extractable fraction from 18 acidic mining lakes. The lakes are exposed to a permanent supply of pyritegenous ferrous iron from adjacent ground water. In 3 of the lakes the suspended matter was fractionated using ultra filtration and analyzed with respect to their mineral composition. In addition, stability experiments with synthetic schwertmannite were performed. The examined lake surface waters were O₂-saturated and have sulfate concentrations (10.3 ± 5.5 mM) and pH values (3.0 ± 0.6) that are characteristic for the stability window of schwertmannite. Geochemical modeling implied that i) the waters were saturated with respect to schwertmannite, which controlled the activity of Fe³⁺ and sulfate, and ii) a redox equilibrium exists between Fe²⁺ and schwertmannite. In the uppermost sediment layers (1 to 5 cm depth), schwertmannite was detectable in 16 lakes—in 5 of them by all three methods. FTIR spectroscopy also proved its occurrence in the colloidal fraction (1-10 kDa) in all of the 3 investigated lake surface waters. The stability of synthetic schwertmannite was examined as a function of pH (2-7) by a 1-yr experiment. The transformation rate into goethite increased with increasing pH. Our study suggests that schwertmannite is the first mineral formed after oxidation and hydrolysis of a slightly acidic (pH 5-6), Fe(II)-SO₄ solution, a process that directly affects the pH of the receiving water. Its occurrence is transient and restricted to environments, such as acidic mining lakes, where the coordination chemistry of Fe³⁺ is controlled by the competition between sulfate and hydroxy ions (i.e. mildly acidic).     

Distribution of bacterial and archaeal ether lipids in soils and surface sediments of Tibetan lakes: Implications for GDGT-based proxies in saline high mountain lakes

Bacterial and archaeal lipids, such as glycerol dialkyl glycerol tetraethers (GDGTs) and dialkyl glycerol diethers, are increasingly used as proxies for specific environmental parameters, such as air temperature and soil pH in lacustrine environments. Little is known, however, about the distribution and applicability of bacterial and archaeal lipids on the Tibetan Plateau. We investigated nine different watersheds across the plateau by way of sediments from lakes and rivers, as well as the surrounding soils. Our transect study included a salinity gradient and focused on saline lakes, which are rarely examined. We analyzed archaeal isoprenoid (i) and bacterial branched (b) GDGTs, as well as archaeol to trace their sources and environmental factors, influencing their distributions. We could show that iGDGTs were produced in situ and bGDGTs were primarily soil-derived although we could not exclude in situ production of bGDGTs in the lakes. The most important environmental variables correlating with GDGT distributions were temperature and salinity. Bacterial GDGT distributions correlated mainly with salinity, while archaeal lipid distributions correlated with temperature. Based on the correlation of methylation (MBT′) and cyclisation (CBT) indices of bGDGTs with pH and mean annual air temperature (MAAT), we established local calibrations for the Tibetan lakes. TEX₈₆ could also be applied to reconstruct temperature, which was strongly biased towards measured summer lake water temperature, indicating enhanced production of iGDGTs in the summer months. Existing proxies show, therefore, potential for palaeoclimate reconstruction on the Tibetan Plateau if local calibrations are applied.     

Concentration of trace elements in small lakes of the Ingoda basin (Chita Region,Russia)

By the example of the Ingoda basin (Transbaikalia) including a system of small lakes, the role of two leading processes of concentration of trace elements in small reservoirs (water–rock interaction and evaporation) has been estimated. It is shown that the accumulation of U, As, Se, Sb, and Ge does not depend on the kind of concentration. Their contents increase linearly with total dissolved solids in both lake and feeding waters. Accumulation of Sc, V, Y, Th, REE, and W is mainly due to evaporation, with their maximum concentration by three to four orders of magnitude. Only U, W, and REE, whose contents in the lakes reach n?100 μg/L, are of practical interest.     

The genesis of sandstone‐type uranium deposits in the Ordos Basin,NW China: constraints provided by fluid inclusions and stable isotopes

Quartz from sandstone‐type uranium deposits in the east part of the Ordos Basin contains abundant secondary fluid inclusions hosted along sealed fractures or in overgrowths. These inclusions consist mainly of water with NaCl, KCl, CO₂ (135–913 ppm) and trace amounts of CO (0.22–16.8 ppm), CH₄ (0.10–1.38 ppm) and [SO₄]^2? (0.35–111 ppm). Homogenization temperatures of the studied fluid inclusions range from 90 to 210°C, with salinities varying from 0.35 to 12.6 wt‐% (converted to NaCl wt%), implying multiple stages of thermal alteration. Although high U is associated with a high homogenization temperature in one case, overall U mineralization is not correlated with homogenization temperature nor with salinity. The H and O isotopic compositions of fluid inclusions show typical characteristics of formation water, with δ¹⁸O ranging from 9.8 to 12.3‰ and δD from 26.9 to ?48.6‰, indicating that these fluid inclusions are mixtures of magmatic and meteoric waters. The oxygen isotope ratios of carbonates in cement are systematically higher than those of the fluid inclusions. Limited fluid inclusion‐cement pairs show that the oxygen closely approaches equilibrium between water and aragonite at 150°C. Highly varied and overall negative δ¹³C in calcite from cement implies different degrees of biogenetic carbon involvement. Correlations between U in bulk rocks and trace components in fluid inclusions are lacking; however, high U contents are typically coupled with high [SO₄]^2?, implying pre‐enrichment of oxidized materials in the U mineralization layer. All these relationships can be plausibly interpreted to indicate that U (IV), [SO₄]^2? as well as Na, K were washed out from the overlying thick sandstone by oxidizing meteoric water, and then were reduced by reducing agents, such as CH₄ and petroleum, likely from underlying coal and petroleum deposits, and possibly also in situ microbes at low temperatures.     

Uranium series disequilibrium in a young surficial uranium deposit,northeastern Washington,U.S.A.

A recently discovered ore-grade accumulation of U in organic-rich sediments of late Quaternary age provides an opportunity for studying the early association of U, U-daughters, and organic matter in a natural setting. The U occurs in valley-fill sediments of peat, peaty clay, silt, and sand along the north fork of Flodelle Creek, Stevens County, Washington. Radiometric techniques (delayed neutron, high-resolution gamma-ray spectrometry, thin-source alpha spectrometry) were employed to determine the abundance and distribution of U-series nuclides, the extent of secular equilibrium within the U decay series, and the apparent U-series ages of U incorporation.Sixteen lithologically distinct intervals were sampled from a 292 cm core. Uranium contents range from 140 to 2790 ppm and are positively correlated with organic contents. Measured alpha activity ratios of ²³⁴U/²³⁸U (1.31–1.38) are very similar to those reported in coexisting waters, suggesting a rather constant isotopic composition of introduced U. Much lower Th contents of <10–40 ppm are controlled by the type and abundance of silicate detritus. The youth of the host sediments (<15 000 a) and the paucity of associated radioactivity suggested large excesses of U relative to radioactive daughters and such excesses were observed, particularly in the shallowest intervals. Apparent ages of U emplacement determined by the (alpha) activity ratio of ²³⁰Th daughter to ²³⁴U parent show a general increase with depth and fair agreement with estimated depositional ages. This observation suggests dominantly syndepositional or early post depositional emplacement of U followed by decay-generated buildup of ²³⁰Th daughter with time. However, interval by interval comparisons of the relative abundances of other daughters, particularly ²²⁶Ra and ²¹⁰Pb, indicate variability caused by processes other than closed-system growth and decay, probably because chemically diverse daughters that are decay-generated in situ have differing mobilities and because upwelling ground water continuously adds more U and minor amounts of daughters. If ²³⁰Th is considered the least susceptible to these modifications, the data suggest some addition of ²³⁴U in the deepest intervals and some loss of ²²⁶Ra and/or gain of ²²²Rn throughout the studied core.     

The solubility control of rare earth elements in natural terrestrial waters and the significance of PO 4 3− and CO 3 2− in limiting dissolved rare earth concentrations: A review of recent information

Rare earth element (REE) concentrations in alkaline lakes, circumneutral pH groundwaters, and an acidic freshwater lake were determined along with the free carbonate, free phosphate, and free sulfate ion concentrations. These parameters were used to evaluate the saturation state of these waters with respect to REE phosphate and carbonate precipitates. Our activity product estimates indicate that the alkaline lake waters and groundwaters are approximately saturated with respect to the REE phosphate precipitates but are significantly undersaturated with respect to REE carbonate and sulfate precipitates. On the other hand, the acidic lake waters are undersaturated with respect to REE sulfate, carbonate, and phosphate precipitates. Although carbonate complexes tend to dominate the speciation of the REEs in neutral and alkaline waters, our results indicate that REE phosphate precipitates are also important in controlling REE behavior. More specifically, elevated carbonate ion concentrations in neutral to alkaline natural waters tend to enhance dissolved REE concentrations through the formation of stable REE-carbonate complexes whereas phosphate ions tend to lead to the removal of the REEs from solution in these waters by the formation of REE-phosphate salts. Removal of REEs by precipitation as phosphate phases in the acid lake (pH=3.6) is inconsequential, however, due to extremely low [PO ₄ ^3– ] _F concentrations (i.e., 10^–23 mol/kg).     

Hydrochemical and stable isotopic investigation of groundwater quality and its sustainability for irrigation in the Hammamet-Nabeul basin,northeastern Tunisia

The major ion hydrochemistry, sodium absorption ratio (SAR), sodium percentage, and isotopic signatures of Hammamet-Nabeul groundwaters were used to identify the processes that control the mineralization, irrigation suitability, and origin of different water bodies. This investigation highlights that groundwater mineralization is mainly influenced by water-rock interaction and pollution by the return flow of irrigation water. The comparison of groundwater quality with irrigation suitability standards proves that most parts of groundwater are unacceptable for irrigation and this long-term practice may result in a significant increase of the salinity and alkalinity in the soils. Based on isotopic signatures, the shallow aquifer groundwater samples were classified into (i) waters with depleted δ¹⁸O and δ²H contents, highlighting recharge by modern precipitation, and (ii) waters with enriched stable isotope contents, reflecting the significance of recharge by contaminated water derived from the return flow of evaporated irrigation waters. The deep-aquifer groundwater samples were also classified into (i) waters with relatively enriched isotope contents derived from modern recharge and mixed with shallow-aquifer groundwater and (ii) waters with depleted stable isotope contents reflecting a paleoclimatic origin. Tritium data permit to identify three origins of recharge, i.e., contemporaneous, post-nuclear, and pre-nuclear. Carbon-14 activities demonstrate the existence of old paleoclimatic recharge related to the Holocene and Late Pleistocene humid periods.     

Hydrogeochemistry of thermal and mineralized waters in the Diyadin (Ağri) area,Eastern Turkey

The Diyadin Geothermal area, located in the eastern part of Anatolia (Turkey) where there has been recent volcanic activity, is favorable for the formation of geothermal systems. Indeed, the Diyadin geothermal system is located in an active geodynamic zone, where strike-slip faults and tensional cracks have developed due to N–S regional compression. The area is characterized by closely spaced thermal and mineralized springs, with temperatures in the range 30–64 °C, and flowrates 0.5–10 L/s. Thermal spring waters are mainly of Ca(Na)-HCO₃ and Ca(Mg)-SO₄ types, with high salinity, while cold groundwater is mostly of Ca(Na, Mg)-HCO₃ type, with lower salinity. High contents of some minor elements in thermal waters, such as F, B, Li, Rb, Sr and Cs probably derive from enhanced water–rock interaction.Thermal water samples collected from Diyadin are far from chemical equilibrium as the waters flow upward from reservoirs towards spring vents and possibly mix with cooler waters. The temperatures of the deep geothermal reservoirs are estimated to be between 92 and 156 °C in Diyadin field, based on quartz geothermometry, while slightly lower estimates are obtained using chalcedony geothermometers. The isotopic composition of thermal water (δ¹⁸O, δ²H, δ³H) indicates their deep-circulating meteoric origin. The waters are likely to have originated from the percolation of rainwater along fractures and faults to the deep hot reservoir. Subsequent heating by conduction due to the presence of an intrusive cupola associated with the Tendurek volcano, is followed by the ascent of deep waters to the surface along faults and fractures that act as hydrothermal conduits.Modeling of the geothermal fluids indicates that the fluid is oversaturated with calcite, aragonite and dolomite, which matches travertine precipitation in the discharge area. Likewise, the fluid is oversaturated with respect to quartz, and chalcedony indicating the possibility of siliceous precipitation near the discharge areas. A conceptual hydro-geochemical model of the Diyadin thermal waters based on the isotope and chemical analytical results, has been constructed.