Estimating the Density and Compressibility of Seawater to High Temperatures Using the Pitzer Equations

The density and compressibility of seawater solutions from 0 to 95 °C have been examined using the Pitzer equations. The apparent molal volumes (X = V) and compressibilities (X = κ) are in the form $$ X_{\phi } = \bar{X}^{0} + A_{X} I/(1.2 \, m)\ln (1 + 1.2 \, I^{0.5} ) + \, 2{\text{RT }}m \, (\beta^{(0)X} + \beta^{(1)X} g(y) + C^{X} m) $$ where $ \bar{X}^{0} $ is the partial molal volume or compressibility, I is the ionic strength, m is the molality of sea salt, A_X is the Debye–Hückel slope for volume (X = V) or adiabatic compressibility (X = κ _s), and g(y) = (2/y ²)[1 ? (1 + y) exp(?y)] where y = 2I ^0.5. The values of the partial molal volume and compressibility ( $ \bar{X}^{0} $ ) and Pitzer parameters (β ^(0)X , β ^(1)X and C ^X ) are functions of temperature in the form $$ Y^{X} = \sum_{i} a_{i} (T-T_{\text{R}} )^{i} $$ where a _i are adjustable parameters, T is the absolute temperature in Kelvin, and T _R = 298.15 K is the reference temperature. The standard errors of the seawater fits for the specific volumes and adiabatic compressibilities are 5.35E?06 cm³ g^?1 and 1.0E?09 bar^?1, respectively. These equations can be combined with similar equations for the osmotic coefficient, enthalpy and heat capacity to define the thermodynamic properties of sea salt to high temperatures at one atm. The Pitzer equations for the major components of seawater have been used to estimate the density and compressibility of seawater to 95 °C. The results are in reasonable agreement with the measured values (0.010E?03 g cm^?3 for density and 0.050E?06 bar^?1 for compressibility) from 0 to 80 °C and salinities from 0 to 45 g kg^?1. The results make it possible to estimate the density and compressibility of all natural waters of known composition over a wide range of temperature and salinity.     

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.     

Preparation and solubility of northupite from brine and its adsorption properties for Cu(II) and Cd(II) in seawater

The mineral northupite Na₃Mg(CO₃)₂Cl was synthesized from a solar Adriatic seawater brine pond to which Na₂CO₃ was added at 373°K. The precipitated northupite had a surface area (P) of 6.0 ± 0.4 m²g⁻¹, and the thermodynamic solubility product was estimated to be log K Na₃Mg(CO₃)₂Cl = −4.8 ± 0.3 at 25°C. This value was used to calculate the interfacial energy (σ = 50 erg cm⁻²) for the homogeneous nucleation of northupite. The solubility constant determined in this study has been used to examine the saturation state of Mahega Lake and Lake Katwe (Uganda). The waters from Lake Katwe were found to be supersaturated with respect to northupite.The adsorption of Cu and Cd onto northupite particles was studied in seawater. Both metals are strongly adsorbed. Adsorption constants and the specific area of northupite occupied by Cd and Cu using Langmuir adsorption isotherms and equilibrium constants for surface complex formation have been determined.     

Direct and Indirect pCO2 Measurements in a Wide Range of pCO2 and Salinity Values (The Scheldt Estuary)

Recent improvements in both Infra-red spectroscopy and equilibrator techniqueshave allowed to determine, for the first time, pCO₂using simultaneously and continuously both the direct and indirect methods in an estuary where pCO₂ values range from 500 to 8500 atm and salinity from 0 to 30. Our results show that both methods are in excellent agreement in the wholeestuary (r² = 0.999, n = 1075, p < 0.0001). Thus, the NBS (US National Bureau of Standards) scale, although inadequate for seawater samples, is appropriate for estuarine waters and can be applied with confidence to calculate pCO₂.     

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–.     

Solubility of rhodochrosite (MnCO3) in water and seawater

The solubility product of rhodochrosite (MnCO₃) was measured in seawater, deionized water and dilute NaCl solutions. The solubility product extrapolated to infinite dilution at 25.0 C was (2.60 ± 0.07)× 10^?11. The stoichiometric solubility product measured in seawater of 34.27%. salinity was (3.24 ± 0.23) × 10^?9 at 25.0 C and (2.28 ± 0.24) × 10^?9 at 3.3 C. The stoichiometric solubility product is in good agreement with the value calculated from an ion association model. The enthalpy of the reaction is in fair agreement with the estimated value.     

Hydrogeochemistry and isotope techniques to determine water interactions in groundwater-dependent shallow lakes,Wet Pampa Plain,Argentina

This paper gives an account of the implementation of hydrochemical and isotopic techniques to identify and explain the processes that govern solute exchange in two groundwater-dependent shallow lakes in the Southeastern Pampa Plain of Argentina. Water samples (lakes, streams, spring water and groundwater) for hydrochemical and stable isotopic determination were collected and the main physical–chemical parameters were measured. The combination of stable isotope data with hydrogeochemical techniques was used for the identification of sources and preferential recharge areas to these aquatic ecosystems which allowed the explanation of the lake water origin. The hydrochemical processes which explain Los Padres Lake water chemistry are evaporation from groundwater, CO₂ input, calcite dissolution, Na⁺ release by Ca²⁺ and Mg²⁺ exchange, and sulfate reduction. The model that best aligns with La Brava Lake hydrochemical constraints includes: mixing, CO₂ and calcite dissolution, cationic exchange with Na⁺ release and Mg²⁺ adsorption, and to a lesser extent, Ca/Na exchange. This model suggests that the fractured aquifer contribution to this water body is greater than 50 %. An isotopic-specific fingerprint for each lake was identified, finding a higher evaporation rate for La Brava Lake compared to Los Padres Lake. Isotopic data demonstrate the importance of these shallow lakes as recharge areas to the regional aquifer, becoming areas of high groundwater vulnerability. The Tandilia Range System, considered in many hydrogeological studies as the impermeable bedrock of the Pampean aquifer, acts as a fissured aquifer in this area, contributing to low salinity waters and with a fingerprint similar to groundwater isotopic composition.     

Changes in water chemistry along the newly formed High Arctic fluvial–lacustrine system of the Brattegg Valley (SW Spitsbergen,Svalbard)

Changes in water chemistry along the High Arctic fluvial–lacustrine system located in Wedel Jarlsberg Land in the SW Spitsbergen (Svalbard) were investigated during the summer season of 2010 and 2011. The newly formed river–lake system consists of three lakes connected with the Brattegg River. The first bathymetric measurements of these lakes were made by the authors in 2010. The Brattegg River catchment represents a partly glaciered Arctic water system. The studied lakes are characterized by low mineralization and temperature of water. The value of the electrolytic conductivity (EC) ranges from 30.2 to 50.5 μS cm^?1 and the temperature of surface water from 1.5 to 7.8 °C. The temperature increase takes place downstream starting from Upper Lake to the outflow from Myrktjørna Lake. The waters of lakes have higher temperatures than the stream. The predominant ions are HCO₃ ^? (up to 16.5 mg L^?1), Cl^? (6.66–8.53 mg L^?1), Ca²⁺ (2.40–4.45 mg L^?1) and Na⁺ (2.65–3.36 mg L^?1). The highest values of ammonium and DOC found in the lowest Myrktjørna Lake seem to be related to the presence of aquatic organisms and also birds. From the group of 10 analyzed microelements, increased concentrations of aluminum, up to almost 500 μg L^?1, are present in the lakes’ water. Water isotopic composition ranges for δ¹⁸O and δ²H, from ?10.6 to ?10.9‰ and from ?70.8 to ?72.3‰, respectively. The vertical zonality of lake waters is manifested in a decrease in the temperature and increase in EC and chemical elements concentrations.     

The pK1 of TRISH+ in Na-K-Mg-Ca-Cl-SO4 brines—pH scales

The stoichiometric dissociation constant, pK¹ of TRISH⁺ has been determined in NaCl, KCl, MgCl₂ and CaCl₂ solutions to an ionic strength of 6 molal. The results have been used to derive Pitzer coefficients for the interactions of TRIS with Na⁺, K⁺, Mg²⁺ and Ca²⁺ ions. These results can be used to determine the pK¹ of TRISH⁺ in mixed brines which can be used to calibrate pH electrodes. Measurements of pK¹ of TRISH⁺ in mixtures of NaCl-MgCl₂, NaCl-CaCl₂, NaCl-Na₂SO₄, KCl-MgCl₂ and KCl-CaCl₂, artificial seawater and Dead Sea waters were made to determine the reliability of the Pitzer coefficients. The estimated values were found to be in good agreement with the measured values provided corrections were made for the interactions of H⁺ with SO²⁻₄. It now is possible to use dilute solutions of TRIS and TRISH⁺ to make buffers that can be used to make reproducible pH measurements in brines.     

Pollution records from sediments of three lakes in New York State

Sediment core segments from Sylvan Lake, Lake Champlain and Lake Canadarago were dated radiometrically with ²¹⁰Pb and ¹³⁷Cs. Their respective sedimentation rates were determined to be 0.11, 0.14 and 0.52 g cm^?2 yr^?1. For the two lakes of lower sedimentation the variations of selected elemental abundances as function of depth were analyzed. Two groupings were found: Al, K, Ti, Rb and Zr were correlated among themselves but reflected different variations in the input of terrigenous erosion material to the lakes. The Cu, Zn and Pb correlated among themselves showed similar depth dependence with increasing concentrations toward the top which can be attributed to cultural pollution. Recent ‘excess’ fluxes to the sediments above the natural contribution by clastic material were derived for the location of the cores, which for Cu, Zn and Pb amounted to 3.8, 24 and 16 μg cm^?2 yr^?1 respectively for Sylvan Lake and 4.9, 20 and 16 μg cm^?2 yr^?1 for Lake Champlain. The corresponding ²¹⁰Pb flux was 3.3 and 2.3 dpm cm^?2 yr^?1, respectively for the two lakes.Approximate residence times in the water column were obtained for trace metals at the Lake Champlain location. Short residence times estimated for Pb (< 0.15 yr) and Cu (< 0.4 yr) indicate fast removal, whereas those for Zn (1.0 ± 0.3 yr) and Cr (2.0 ± 0.5 yr) appeared to be dominated by the water residence time.     

Trace metal deposition and mobility in the sediments of two lakes near Sudbury,Ontario

The accumulation and mobility of Fe, Mn, Al, Cu, Ni and Pb in the sediments of two lakes (Clearwater, pH 4.5; and McFarlane, pH 7.5) near Sudbury, Ontario have been investigated. The Al, Cu and Ni concentrations are expectedly relatively high in the overlying waters of Clearwater Lake and much lower for Al and Cu in McFarlane Lake. The low trace metal concentrations found in the anoxic porewaters of Clearwater Lake could be explained by a sharp increase in porewater pH concomitant with SO₄² reduction and H₂S production within the first 1–2 cm of the sediments, which has conceivably led to the precipitation of mineral phases such as AL(OH)₃, NiS, and CuS. In both lakes, Fe concentrations in anoxic porewaters appear to be controlled by FeS and/or FeCO₃ formation. Solubility calculations also indicate MnCO₃ precipitation in McFarlane Lake. In Clearwater Lake, however, both porewater and total Mn were relatively low, a possible result of the continuous loss of Mn(II) through the acidic interface. It is suggested that upwardly decreasing total Mn profiles resulting from the removal of Mn from the top sediment layers under acidic conditions may constitute a reliable symptom of recent lake acidification.The downward diffusion of AI, Cu and Ni from the overlying water to the sediments has been estimated from their concentration gradients at the interface and compared to their total accumulation rates in the sediments. In both lakes the diffusion of Al is negligible compared to its accumulation rate. However, diffusion accounts for 24–52% of the accumulation of Cu in the sediments of Clearwater Lake, but appears negligible in McFarlane Lake. The downward diffusive flux of Ni is important and may explain 76–161% of the estimated Ni accumulation rate in Clearwater Lake, and 59% in McFarlane Lake. The porewater Cu and Ni profiles suggest that the subsurface sedimentary trace metal peaks observed in Clearwater Lake (as in other acid lakes) may not be caused by sediment leaching or by a recent reduction in sedimentation but may have a diagenetic origin instead. Diffusion to the sediments thus appears to be an important and previously overlooked trace metal deposition mechanism, particularly in acid lakes.     

Origin of groundwater salinity (current seawater vs. saline deep water) in a coastal karst aquifer based on Sr and Cl isotopes. Case study of the La Clape massif (southern France)

In this study a typical coastal karst aquifer, developed in lower Cretaceous limestones, on the western Mediterranean seashore (La Clape massif, southern France) was investigated. A combination of geochemical and isotopic approaches was used to investigate the origin of salinity in the aquifer. Water samples were collected between 2009 and 2011. Three groundwater groups (A, B and C) were identified based on the hydrogeological setting and on the Cl⁻ concentrations. Average and maximum Cl⁻ concentrations in the recharge waters were calculated (Cl_Ref. and Cl_Ref.Max) to be 0.51 and 2.85 mmol/L, respectively). Group A includes spring waters with Cl⁻ concentrations that are within the same order of magnitude as the Cl_Ref concentration. Group B includes groundwater with Cl⁻ concentrations that range between the Cl_Ref and Cl_Ref.Max concentrations. Group C includes brackish groundwater with Cl⁻ concentrations that are significantly greater than the Cl_Ref.Max concentration. Overall, the chemistry of the La Clape groundwater evolves from dominantly Ca–HCO₃ to NaCl type. On binary diagrams of the major ions vs. Cl, most of the La Clape waters plot along mixing lines. The mixing end-members include spring waters and a saline component (current seawater or fossil saline water). Based on the Br/Cl_molar ratio, the hypothesis of halite dissolution from Triassic evaporites is rejected to explain the origin of salinity in the brackish groundwater.Groundwaters display ⁸⁷Sr/⁸⁶Sr ratios intermediate between those of the limestone aquifer matrix and current Mediterranean seawater. On a Sr mixing diagram, most of the La Clape waters plot on a mixing line. The end-members include the La Clape spring waters and saline waters, which are similar to the deep geothermal waters that were identified at the nearby Balaruc site. The ³⁶Cl/Cl ratios of a few groundwater samples from group C are in agreement with the mixing hypothesis of local recharge water with deep saline water at secular equilibrium within a carbonate matrix. Finally, PHREEQC modelling was run based on calcite dissolution in an open system prior to mixing with the Balaruc type saline waters. Modelled data are consistent with the observed data that were obtained from the group C groundwater. Based on several tracers (i.e. concentrations and isotopic compositions of Cl and Sr), calculated ratios of deep saline water in the mixture are coherent and range from 3% to 16% and 0% to 3% for groundwater of groups C and B, respectively.With regard to the La Clape karst aquifer, the extension of a lithospheric fault in the study area may favour the rise of deep saline water. Such rises occur at the nearby geothermal Balaruc site along another lithospheric fault. At the regional scale, several coastal karst aquifers are located along the Gulf of Lion and occur in Mezosoic limestones of similar ages. The ⁸⁷Sr/⁸⁶Sr ratios of these aquifers tend toward values of 0.708557, which suggests a general mixing process of shallow karst waters with deep saline fossil waters. The occurrence of these fossil saline waters may be related to the introduction of seawater during and after the Flandrian transgression, when the highly karstified massifs invaded by seawater, formed islands and peninsulas along the Mediterranean coast.     

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.     

Origin and migration of brines from Paleozoic strata in Central Tarim,China: constraints from 87Sr/86Sr, δD, δ18O and water chemistry

Chemistry of major and minor elements, ⁸⁷Sr/⁸⁶Sr, δD, and δ¹⁸O of oilfield waters, and ⁸⁷Sr/⁸⁶Sr of whole rock were measured from Paleozoic strata in the Central Tarim basin, NW China. The aim is to elucidate the origin and migration of formation water and its relation to petroleum migration. High salinity oilfield waters in Carboniferous, Silurian and Ordovician reservoirs have maintained the same Na/Cl ratio as seawater, indicative of subaerially evaporated seawater. Two possible sources of evaporitic water are Carboniferous (C_II) and Cambrian, both of which contain evaporitic sediments. Geographic and stratigraphic trends in water chemistry suggest that most of the high salinity water is from the Cambrian. Strontium, H and O isotopes as well as ion chemistry indicate at least 3 end member waters in the basin. High-salinity Cambrian evaporitic water was expelled upward into Ordovician, Silurian and Carboniferous reservoirs along faults and fractures during compaction and burial. Meteoric water has likely invaded the section throughout its history as uplift created subaerial unconformities. Meteoric water certainly infiltrated Silurian and older strata during development of the C_III unconformity and again in recent times. Modern meteoric water enters Carboniferous strata from the west and flows eastward, mixing with the high salinity Cambrian water and to a lesser degree with paleometeoric water. The third end member is highly radiogenic, shale-derived water which has migrated eastward from the Awati Depression to the west. Enrichment of Ca and Sr and depletion of K, Mg, and SO₄ relative to the seawater evaporation trajectory suggest waters were affected by albitization of feldspars, dolomitization, illitization of smectite, and SO₄ reduction. The mixing of meteoric water occurred subsequently to seawater evaporation, main water-rock interactions, and brine migration. The direction of brine migration is consistent with that of petroleum migration, suggesting water and petroleum have followed the same migration pathways.     

The effect of pressure on the ionization of boric acid in sodium chloride and seawater from molal volume data at 0 and 25°C

The apparent molal volume, φ_V of boric acid, B(OH)₃ and sodium borate, NaB(OH)₄, have been determined in 35%. salinity seawater and 0·725 molal NaCl solutions at 0 and 25°C from precise density measurements. Similar to the behavior of nonelectrolytes and electrolytes in pure water, the φ_V of B(OH)₃ is a linear function of added molality and the φ_V of NaB(OH)₄ is a linear function of the square root of added molarity in seawater and NaCl solutions. The partial molal volumes, $\text{V}\text{?}\text{1}$, of B(OH)₃ and NaB(OH)₄ in seawater and NaCl were determined from the φ_V's by extrapolating to infinite dilution in the medium. The $\text{V}\text{?}\text{1}$ of B(OH)₃ is larger in NaCl and seawater than pure water apparently due to the ability of electrolytes to dehydrate the nonelectrolyte B(OH)₃. The $\text{V}\text{?}\text{1}$ of NaB(OH)₄ in itself, NaCl and seawater is larger than the expected value at 0·725 molal ionic strength due to ion pair formation [Na⁺ + B(OH)₄^? → NaB(OH)₄⁰]. The volume change for the formation of NaB(OH)₄⁰ in itself and NaCl was found to be equal to 29·4 ml mol^?1 at 25°C and 0·725 molal ionic strength. These large $\text{Δ}\text{V}\text{?}\text{1}$'s indicate that at least one water molecule is released when the ion pair is formed [Na⁺ + B(OH)₄^? → H₂O + NaOB(OH)₂⁰]. The observed $\text{V}\text{?}\text{1}$ in seawater and the $\text{Δ}\text{V}\text{?}\text{1}$ (NaB⁰) in water and NaCl were used to estimate $\text{Δ}\text{V}\text{?}\text{1 (MgB}{}^{\mathrm{+}}\text{) = Δ}\text{V}\text{?}\text{1 (CaB}{}^{\mathrm{+}}\text{) = 38·4 ml mol}{}^{\mathrm{?1}}$ for the formation of MgB⁺ and CaB⁺. The volume change for the ionization of B(OH)₃ in NaCl and seawater was determined from the molal volume data. Values of $\text{Δ}\text{V}\text{?}\text{1 = ?29·2 and ?25·9 ml mol}{}^{\mathrm{?1}}$ were found in seawater and $\text{Δ}\text{V}\text{?}\text{1 = ?21·6 and ?26·4}$ in NaCl, respectively, at 0 and 25°C. The effect of pressure on the ionization of B(OH)₃ in NaCl and seawater at 0 and 25°C determined from the volume change is in excellent agreement with direct measurements in artificial seawater (culberson and Pytkowicz, 1968; Disteche and Disteche, 1967) and natural seawater (Culberson and Pytkowicz, 1968).     

The Helium Isotopic Chemistry of Lake Bonney, Taylor Valley, Antarctica: Timing of Late Holocene Climate Change in Antarctica

To better understand the long-term climate history of Antarctica, we studied Lake Bonney in Taylor Valley, Southern Victoria Land (78°S). Helium isotope ratios and He, Ne, Ar and N₂ concentration data, obtained from hydrocasts in the East (ELB) and West (WLB) Lobes of Lake Bonney, provided important constraints on the lakes Holocene evolution. Based on very low concentrations of Ar and N₂ in the ELB bottom waters, ELB was free of ice until 200 ± 50 years ago. After which, low salinity water flowing over the sill from WLB to ELB, covered ELB and formed a perennial ice cover, inhibiting the exchange of gases with the atmosphere. In contrast to the ELB, the WLB retained an ice cover through the Holocene. The brine in the WLB bottom waters has meteoric N₂ and Ar gas concentrations indicating that it has not been significantly modified by atmospheric exchange or ice formation. The helium concentrations in the deep water of WLB are the highest measured in non-thermal surface water. By fitting a diffusional loss to the ³He/⁴He, helium, and Cl profiles, we calculate a time of 3000 years for the initiation of flow over the sill separating the East and West Lobes. To supply this flux of helium to the lake, a helium-rich sediment beneath the lake must be providing the helium by diffusion. If at any time during the last million years the ice cover left WLB, there would be insufficient helium available to provide the current flux to WLB. The variations in water levels in Lake Bonney can be related to climatic events that have been documented within the Southern Victoria Land region and indicate that the lakes respond significantly to regional and, perhaps, global climate forcing.     

Geochemical evidence of seawater intrusion into a coastal geothermal field of central Greece: example of the Thermopylae system

Thermal water of Thermopylae and from other geothermal fields located in the southern part of the Sperchios basin (central Greece) are characterized by high salinity (total dissolved salts, or TDS, range from 1.2 to 30.3 g L⁻¹) associated with a degassing of CO₂. To determine the mineralization processes, geochemical and isotopic investigations (major elements, ¹⁸O, ²H and ¹³C) have been carried out upon 17 thermal waters from springs and boreholes. This study emphasizes that all the thermal waters result from the mixing of a seawater end-member, several fresh water components depending on the field location, and a mantle-derived CO₂ rising upward through an E–W fault system. The seawater identified in the thermal mixture is likely to be evolved Aegean seawater (ASW). Once intruded into the basin sediments, the trapped seawater has its chemical content modified by both water–rock interactions and massive dissolution of the deep CO₂ (pCO₂ of 10^0.5 atm). The modelling performed with PHREEQC indicates that the anomalous major ion ratios measured in the so-called evolved ASW are explained by the dissolution of calcite and dolomitization process associated to precipitation of gypsum within the thermal aquifer.     

Vertical stability and the Brunt-Väisäla frequency of deep natural waters by the example of Lake Baikal,Lake Tanganyika,and the World Ocean

Theoretical analysis, calculations, and comparison with the results of observations in Lake Baikal, Lake Tanganyika, and the World Ocean are performed for the vertical stability E and the Brunt-Väisäla frequency N in the form of N ² with regard to all components (at the constant temperature T and the salinity S, the common adiabatic form at T, S Const). The adiabatic stability E _ad and the Väisäla frequency N in the form of N _ad ² are always positive; at a change from the inverse to the direct temperature stratification, they have deep minimums reaching 10^?16 m^?1 and 10^?15 s^?2 and less; the minimums have the form of a special point, a reversal point of the first kind called a “cusp.” The reality of these reversal points is confirmed by the analysis of the investigation procedure, comparison with the results of previous theoretical (Sherstyankin, et al., 2007), and experimental (observations in Baikal, Shimaraev et al., 1994) works. The features of vertical profiles of E _ad , E andN _ad ² , N ², as well as the layers where the Brunt-Väisäla frequency is less than the inertial frequency, are studied. The analysis with regard to all components of the stability E _ad and the Brunt-Väisäla frequency N makes a great contribution to understanding of mixing processes in theoretical and experimental investigations; it is valid in all reservoirs of the Earth with inverse and direct temperature stratification, including Lake Baikal, Lake Tanganyika, and the World Ocean.