Geochemistry of the acid Kawah Putih lake, Patuha Volcano, West Java, Indonesia

Kawah Putih is a summit crater of Patuha volcano, West Java, Indonesia, which contains a shallow, 300 m-wide lake with strongly mineralized acid–sulfate–chloride water. The lake water has a temperature of 26–34°C, pH=<0.5–1.3, S^tot=2500–4600 ppm and Cl=5300–12 600 ppm, and floating sulfur globules with sulfide inclusions are common. Sulfur oxyanion concentrations are unusually high, with S₄O₆²⁻+S₅O₆²⁻+S₆O₆²⁻=2400 – 4200 ppm. Subaerial fumaroles (<93°C) on the lake shore have low molar SO₂/H₂S ratios (<2), which is a favorable condition to produce the observed distribution of sulfur oxyanion species. Sulfur isotope data of dissolved sulfate and native sulfur show a significant ³⁴S fractionation (ΔSO₄–S_e of 20‰), probably the result of SO₂ disproportionation in or below the lake. The lake waters show strong enrichments in ¹⁸O and D relative to local meteoric waters, a result of the combined effects of mixing between isotopically heavy fluids of deep origin and meteoric water, and evaporation-induced fractionation at the lake surface. The stable-isotope systematics combined with energy-balance considerations support very rapid fluid cycling through the lake system. Lake levels and element concentrations show strong seasonal fluctuations, indicative of a short water residence time in the lake as well.Thermodynamic modeling of the lake fluids indicates that the lake water is saturated with silica phases, barite, pyrite and various Pb, Sb, Cu, As, Bi-bearing sulfides when sulfur saturation is assumed. Precipitating phases predicted by the model calculations are consistent with the bulk chemistry of the sulfur-rich bottom sediments and their identified mineral phases. Much of the lake water chemistry can be explained by congruent rock dissolution in combination with preferential enrichments from entering fumarolic gases or brines and element removal by precipitating mineral phases, as indicated by a comparison of the fluids, volcanic rocks and lake bed sediment.Flank springs on the mountain at different elevations vary in composition, and are consistent with local rock dissolution as a dominant factor and pH-dependent element mobility. Discharges of warm sulfate- and chloride-rich water at the highest elevation and a near-neutral spring at lower level may contain a small contribution of crater-lake water. The acid fluid-induced processes at Patuha have led to the accumulation of elements that are commonly associated with volcano-hosted epithermal ore deposits. The dispersal of heavy metals and other potentially toxic elements from the volcano via the local drainage system is a matter of serious environmental concern.     

Results of Hydrochemical Studies of Lake Azabach'e (Kamchatka)

The nutrient basis of Lake Azabach'e is studied. The distribution of pH and the concentrations of O₂, P_min, Fe, N–NH⁺ ₄, N–NO^– ₃, Si, and organic forms of N and P are considered. The chemical basis of biological production of Lake Azabach'e is assessed. It is found that the amount of Si is excessive everywhere and that phytoplankton production is limited by phosphate and mineral nitrogen deficiency in virtually equal degrees.     

A theoretical interpretation of ion composition measured on board the ‘Active’ satellite in the European sector during April 10-12, 1990 geomagnetic storm

Ion composition measurements on board the ACTIVE satellite during the recovery phase of a strong geomagnetic storm of 10–12 April 1990 revealed extremely high concentrations (up to 10³ cm⁻³) of the NO⁺, O⁺₂, N⁺₂ molecular ions in the topside F2-region of the European high-latitude zone. Concentrations of O⁺, N⁺, He⁺, H⁺ light ions were slightly decreased relative to prestorm quite conditions. Theoretical calculations were used to analyze the observed variations in ion concentration. Increased neutral temperature and [O₂], [N₂] are shown to be the main reasons for the observed ion concentration variations.     

Evaluation of volcanic gas analysis from surtsey volcano, iceland 1964–1967

Methods used previously to remove compositional modifications from volcanic gas analyses for Mount Etna and Erta'Ale lava lake have bean employed to estimate the gas phase composition at Nyiragongo lava lake, based on samples obtained in 1959. H₂O data were not reported in 11 of the 13 original analyses. The restoration methods have been used to estimate the H₂O contents of the samples and to correct the analyses for atmospheric contamination, loss of sulfur and for pre- and pest-collection oxidation of H₂S, S₂, and H₂. The estimated gas compositions are relatively CO₂-rich, low in total sulfur and reduced. They contain approximately 35–50% CO₂ 45–55% H₂O, 1–2% SO₂, 1–2% H₂., 2–3% CO, 1.5–2.5% H₂S, 0.5% S₂ and 0.1% COS over,he collection temperature range 102° to 960° C. The oxygen fugacities of the gases are consistently about half an order of magnitude below quartz-magnetite-fayalite. The low total sulfur content and resulting low atomic S/C of the Nyiragongo gases appear to be related to the relatively low f_O2 of the crystallizing lava. At temperatures above 800°C and pressures of 1–1.5 k bar, the Nyiragongo gas compositions resemble those observed in primary fluid inclusions believed to have formed at similar temperatures and pressures in nephelines of intrusive alkaline rocks. Cooling to 300°C, with f_O2 buffered by the rock, results in gas compositions very rich in CH₄ (50–70%) and resembling secondary fluid inclusions formed at 200–500°C in alkaline rocks. Below 600°C the gases become supersaturated in carbon as graphite. These inferences are corroborated by several reports of hydrocarbons in plutonic alkaline rocks, and by the presence of CH₄-rich waters in Lake Kivu — a lake on the flanks of Nyiragongo volcano.     

The role of vibrationally excited nitrogen in the formation of the mid-latitude negative ionospheric storms

Millstone Hill ionospheric storm time measurements of the electron density and temperature during the ionospheric storms (15-16 June 1965; 29–30 September 1969 and 17–18 August 1970) are compared with model results. The model of the Earth’s ionosphere and plasmasphere includes interhemispheric coupling, the H⁺, O⁺(⁴S), O⁺(²D), O⁺(²P), NO⁺, O⁺₂ and N⁺₂ ions, electrons, photoelectrons, the electron and ion temperature, vibrationally excited N₂ and the components of thermospheric wind.In order to model the electron temperature at the time of the 16 June 1965 negative storm, the heating rate of the electron gas by photoelectrons in the energy balance equation was multiplied by the factors 5–30 at he altitude above 700 km for the period 4.50-12.00 LT, 16 June 1965. The [O]/[N₂] MSIS-86 decrease and vibrationally excited N₂ effects are enough to account for the electron density depressions at Millstone Hill during the three storms. The factor of 2 (for 27–30 September 1969 magnetic storm) and the & actor 2.7 (for 16–18 August 1970 magnetic storm) reduction in the daytime peak density due to enhanced vibrationally excited N₂ is brought about by the increase in the O⁺+N₂ rate factor.     

水力调控对湖泊甲烷扩散通量的影响

外源引水等水力调控措施常用于湖泊水环境综合整治中,作为人类施加到湖泊显著的外界活动,其对湖泊甲烷(CH4)扩散通量的影响鲜有报道.贡湖湾作为"引江济太"工程长江来水进入太湖的第一站,其CH4通量变化是对水力调控的最好响应.基于2011年11月至2013年8月逐月的野外观测表明,贡湖湾平均CH4扩散排放量为0.073 m...     

Hydrothermal vent waters at 13°N on the East Pacific Rise: isotopic composition and gas concentration

Gas concentrations and isotopic compositions of water have been measured in hydrothermal waters from 13°N on the East Pacific Rise. In the most Mg-depleted samples ( 5 × 10⁻³ moles/kg) the gas concentrations are: 3–4.5 × 10⁻⁵ cm³ STP/kg helium, 0.62–1.24 cm³ STP/kg CH₄, 10.80–16.71 × 10⁻³ moles/kg CO₂. The samples contain large quantities (95–126 cm³/kg) of H₂ and some carbon monoxide (0.26–0.36 cm³/kg) which result from reaction with the titanium sampling bottles. δ¹³C in methane and CO₂ (−16.6 to −19.5 and −4.1 to −5.5 respectively) indicate temperatures between 475 and 550°C, whereas δ¹³C_CO is compatible with formation by reduction of CO₂ on Ti at 350°C close to the sampling temperature.³He/⁴He are very homogeneous at (7.5 ± 0.1)R_A(³He/⁴He = 1.0 × 10⁻⁵) and very similar to already published data as well as CH₄/³He ratios between 1.4 and 2.1 × 10⁶.¹⁸O and D in water show enrichments from 0.39 to 0.69‰ and from 0.62 to 1.49‰ respectively. These values correspond to W/R ratios of 0.4–7. The distinct¹⁸O enrichments indicate that the isotopic composition of the oceans is not completely buffered by the hydrothermal circulations. The³He-enthalpy relationship is discussed in terms of both hydrothermal heat flux and³He mantle flux.     

Chemical composition of fumarolic gases and spring discharges from El Chichòn volcano, Mexico: causes and implications of the changes detected over the period 1998–2000

Since the March–April 1982 eruption of El Chichòn volcano, intense hydrothermal activity has characterised the 1-km-wide summit crater. This mainly consists of mud and boiling pools, fumaroles, which are mainly located in the northwestern bank of the crater lake. During the period 1998–2000, hot springs and fumaroles discharging inside the crater and from the southeastern outer flank (Agua Caliente) were collected for chemical analyses. The observed chemical fluctuations suggest that the physico-chemical boundary conditions regulating the thermodynamic equilibria of the deep rock/fluid interactions have changed with time. The chemical composition of the lake water, characterised in the period 1983–1997 by high Na⁺, Cl⁻, Ca²⁺ and SO₄²⁻ contents, experienced a dramatic change in 1998–1999, turning from a Na⁺–Cl⁻- to a Ca²⁺–SO₄²⁻-rich composition. In June 2000, a relatively sharp increase in Na⁺ and Cl⁻ contents was observed. At the same time, SO₂/H₂S ratios and H₂ and CO contents in most gas discharges increased with respect to the previous two years of observations, suggesting either a new input of deep-seated fluids or local variations of the more surficial hydrothermal system. Migration of gas manifestations, enhanced number of emission spots and variations in both gas discharge flux and outlet temperatures of the main fluid manifestations were also recorded. The magmatic-hydrothermal system of El Chichòn is probably related to interaction processes between a deep magmatic source and a surficial cold aquifer; an important role may also be played by the interaction of the deep fluids with the volcanic rocks and the sedimentary (limestone and evaporites) basement. The chemical and physical changes recorded in 1998–2000 were possibly due to variations in the permeability of the conduit system feeding the fluid discharges at surface, as testified by the migration of gas and water emanations. Two different scenarios can be put forward for the volcanic evolution of El Chichòn: (1) build-up of an infra-crater dome that may imply a future eruption in terms of tens to hundreds of years; (2) minor phreatic–phreatomagmatic events whose prediction and timing is more difficult to constrain. This suggests that, unlike the diminished volcanic activity at El Chichòn after the 1982 paroxistic event, the volcano-hydrothermal fluid discharges need to be more constantly monitored with regular and more frequent geochemical sampling and, at the same time, a permanent network of seismic stations should be installed.     

Preliminary results of seismogeochemical research in China

Several kinds of geochemical anomaly before strong earthquakes have been observed in China since 1966. They include changes in groundwater radon levels, ion content of water (Ca⁺², Mg⁺², Cl^–, SO ₄ ^–2 , F^–), dissolved gases (H₂, CO₂), and gases escaping from the aeration zone through abandoned dry wells (Ar, N₂, CO₂). The radon anomalies may be grouped as long-term and short-term anomalies. Most of the geochemical anomalies observed are characterized by a pattern of increase. The largest amplitude recorded was 37 times the base level. Preliminary study indicates that the types of seismogeochemical anomaly observed prior to strong earthquakes depend on tectonic, geologic, lithologic, and hydrogeological conditions at the monitoring station. Results obtained from modelling experiments on the mechanisms of some anomalies are given.     

Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.     

Nitrogen cycling across the sediment-water interface in an eutrophic,artificially oxygenated lake

Processes controlling the nitrogen (N) exchange between water and sediment in eutrophic Lake Sempach were studied using three different independent methods: benthic flux chambers, interstitial water data and hypolimnetic mass balances. The sediments released NH ₄ ⁺ (1.1–16.1 mmoles m^–2 d^–1), NO ₂ ^- (0.1–0.4 mmoles m^–2 d^–1) and dissolved organic N (<0.25 mmoles m^–2 d^–1). A net NO ₃ ^- consumption (2.4–11.1 mmoles m^–2 d^–1) related to the NO ₃ ^- concentrations in the overlying water was observed in all benthic chamber experiments. The flux of the reactive species NO ₃ ^- and NH ₄ ⁺ was found to depend on hydrodynamic conditions in the water overlying the sediment. For this reason, benthic chambers overestimated the fluxes of inorganic N compared to the other methods. Thus, in short-term flux chamber experiments the sediment may either become a sink or a source for inorganic N depending on the O₂ concentration in the water overlying the sediment and the stirring rate. As demonstrated with a¹⁵NO ₃ ^- experiment, nitrate-ammonification accounted for less than 12% of the total NO ₃ ^- consumption. After six years of artificial oxygenation in Lake Sempach, a decrease in hypolimnetic total inorganic nitrogen (TIN) was observed in the last two years. The occurrence of dense mats of H₂S-oxidizingBeggiatoa sp. indicated micro-aerobic conditions at the sediment surface. Under these conditions, a shorter distance between the ecological niches of nitrifying and denitrifying bacteria, and therefore a faster NO ₃ ^- -transport, can possibly explain the lowering of TIN by enhanced net denitrification.     

Gas geochemistry of the Valles caldera region, New Mexico and comparisons with gases at Yellowstone, Long Valley and other geothermal systems

Noncondensible gases from hot springs, fumaroles, and deep wells within the Valles caldera geothermal system (210–300°C) consist of roughly 98.5 mol% CO₂, 0.5 mol% H₂S, and 1 mol% other components. ³He/⁴He ratios indicate a deep magmatic source (R/R_a up to 6) whereas δ¹³C–CO₂ values (−3 to −5‰) do not discriminate between a mantle/magmatic source and a source from subjacent, hydrothermally altered Paleozoic carbonate rocks. Regional gases from sites within a 50-km radius beyond Valles caldera are relatively enriched in CO₂ and He, but depleted in H₂S compared to Valles gases. Regional gases have R/R_a values ≤1.2 due to more interaction with the crust and/or less contribution from the mantle. Carbon sources for regional CO₂ are varied. During 1982–1998, repeat analyses of gases from intracaldera sites at Sulphur Springs showed relatively constant CH₄, H₂, and H₂S contents. The only exception was gas from Footbath Spring (1987–1993), which experienced increases in these three components during drilling and testing of scientific wells VC-2a and VC-2b. Present-day Valles gases contain substantially less N₂ than fluid inclusion gases trapped in deep, early-stage, post-caldera vein minerals. This suggests that the long-lived Valles hydrothermal system (ca. 1 Myr) has depleted subsurface Paleozoic sedimentary rocks of nitrogen. When compared with gases from many other geothermal systems, Valles caldera gases are relatively enriched in He but depleted in CH₄, N₂ and Ar. In this respect, Valles gases resemble end-member hydrothermal and magmatic gases discharged at hot spots (Galapagos, Kilauea, and Yellowstone).     

The solubility mechanisms of volatiles in silicate melts and their relations to crystal-andesite liquid equilibria

The anionic structure of magmatic liquids has been estimated at 1 atm and at pressures corresponding to those of the upper mantle. These estimates are based predominantly on spectroscopic data on binary metal oxide-silica and ternary metal oxide-silica-alumina melts. Structural information on melt compositions in aluminate-silica joins has been used to provide detailed information on the role of Al³⁺ in natural magma at atmospheric and high pressure.Regardless of pressure, andesitic melts may be described as combinations of chain, sheet, and three-dimensional network units. Nearly all Al³⁺ in the magmatic liquid resides in the three-dimensional network units. This Al³⁺ is locally charge-balanced with Na⁺, K⁺, Ca²⁺, and Mg²⁺. In the latter two cases, Al³⁺ and Si⁴⁺ are ordered, whereas for Na⁺ and K⁺, Si⁴⁺ and Al³⁺ are randomly mixed. Solution of water in natural magma results in the formation of new nonbridging oxygens in addition to OH groups attached to Si⁴⁺ and metal cations.On the basis of determined solution mechanisms of CO₂ and H₂O in silicate melts, thermodynamic properties of HO+CO₂, fluids and hydrous silicate melts and melting phase relations in peridotite-H₂O-CO₂, systems, it is found that natural andesitic magma in equilibrium with spinel Iherzolite in the upper mantle (10–20 kbar) must contain at least 5–7 wt.% H₂O. Andesitic magma with 5–7 wt.% H₂O in solution may be described as a mixture of Al-free three-dimensional units, sheets, and chains with a small proportion (less than 10%) of monomers.     

Multivariate statistical analysis of geochemical data as indicative of the hydrogeochemical evolution of groundwater in a sedimentary rock aquifer system

The study of groundwater hydrogeochemistry of the Paleozoic Basses-Laurentides sedimentary rock aquifer system in Québec produced a large geochemical dataset. Groundwater samples were collected at 153 sites over a 1500 km² study area and analyzed for major and minor ions. The large number of data can lead to difficulties in the integration, interpretation and representation of the results. Two multivariate statistical methods, hierarchical cluster analysis (HCA) and principal components analysis (PCA), were applied to a subgroup of the dataset to evaluate their usefulness to classify the groundwater samples, and to identify geochemical processes controlling groundwater geochemistry. This subgroup consisted of 144 samples and 14 parameters (Ca²⁺, Mg²⁺, Na⁺, K⁺, , Cl⁻, , Fe²⁺, Mn²⁺, Br⁻, Sr²⁺, F⁻, Ba²⁺, HS⁻). Seven geochemically distinct clusters, C1–C7, resulted from the HCA. Samples from clusters C3, C4, C6 and C7 are mostly located in preferential recharge areas. The majority of these samples have Ca–Mg–HCO₃ recharge groundwater (C3, C6, C7) and Na–HCO₃ evolved groundwater (C4). Samples from the other three clusters (C1, C2, C5) are characteristic of an aquifer system under confined conditions. The majority of these samples have Na–HCO₃ evolved groundwater (C1, C5) and Na–Cl ancient groundwater that exhibits elevated concentrations in Br⁻ (C2). In addition to recognizing the importance of hydrogeological conditions on groundwater geochemistry, the distribution of clusters also showed the importance of the geological formations on minor and trace elements, such as Fe²⁺, Mn²⁺, Sr²⁺, F⁻ and Ba²⁺. The first five components of the PCA account for 78.3% of the total variance in the dataset. Component 1 is defined by highly positive loadings in Na⁺, Cl⁻ and Br⁻ and is related to groundwater mixing with Champlain Sea water and solute diffusion from the marine clay aquitard. The high positive loadings in Ca²⁺ and Mg²⁺ of component 2 suggest the importance of dissolution of carbonate rocks in this aquifer system. From their characteristic loadings, the first two components are defined as the “salinity” and “hardness” components, respectively. Components 3–5 are related to more local and geological effects. The integration of the HCA and the PCA, with conventional classification of groundwater types, as well as with the hydrogeological and geological contexts, allowed the division of the region into four main geochemical areas, providing an improved regional picture of the aquifer system dynamics and hydrogeochemical evolution of groundwater. The following factors were recognized as influencing the evolution of groundwater identified in every geochemical area: (1) geological characteristics including sedimentary rock type and till mineralogy; (2) hydrogeological characteristics represented by the level of confinement and the hydraulic gradient; and (3) the geological history including the latest glaciation and the Champlain Sea invasion. With its integrated approach, this hydrogeochemical study contributes to the characterization and understanding of complex groundwater flow systems, and provides an example of the long-term geochemical evolution of hydrogeological systems after a major perturbation, in this case seawater invasion.     

Pollutant Concentrations in Mountain River Waters in the Upper Baksan Area (Prielbrus’e National Park) and Their Seasonal Variations

Materials of expedition studies in 2013 in the Prielbrus’e National Park were used to analyze the concentrations of a wide range of pollutants (SO₄^2-, Cl^?, Na⁺, K⁺, F^?, Mn, Cu, Zn, Pb, Cr, Ni, NO₃^-, NH₄⁺) in the water of mountain rivers forming the main artery of the region, the Baksan R. The analyzed data characterize seasonal variations in pollutant concentrations at seven sampling sections and their dynamics along the river down to the 35th km from the source in different seasons.     

Control of primary productivity and the significance of photosynthetic bacteria in a meromictic kettle lake. Mittlerer Buchensee,West-Germany

During 1986 planktonic primary production and controlling factors were investigated in a small (A₀ = 11.8 · 10³ m², Z_max = 11.5 m) meromictic kettle lake (Mittlerer Buchensee). Annual phytoplankton productivity was estimated to ca 120 gC · m^–2 · a^–1 (1,42 tC · lake^–1 · a^–1). The marked thermal stratification of the lake led to irregular vertical distributions of chlorophylla concentrations (Chla) and, to a minor extent, of photosynthesis (A_z). Between the depths of 0 to 6 m low Chla concentrations (< 7 mg · m^–3) and comparatively high background light attenuation (k_w = 0,525 m^–1, 77% of total attenuation due to gelbstoff and abioseston) was found. As a consequence, light absorption by algae was low (mean value 17,4%) and self-shading was absent.Because of the small seasonal variation of Chla concentrations, no significant correlation between Chla and areal photosynthesis (A) was observed. Only in early summer (June–July) biomass appears to influence the vertical distribution of photosynthesis on a bigger scale. Around 8 m depth, low-light adapted algae and phototrophic bacteria formed dense layers. Due to low ambient irradiances, the contribution of these organisms to total primary productivity was small. Primary production and incident irradiance were significantly correlated with each other (r² = 0.68). Although the maximum assimilation number (P_opt) showed a clear dependence upon water temperature (Q₁₀ = 2.31), the latter was of minor importance to areal photosynthesis.     

Pulsating of the generalized ion and neutral polar winds

A three-dimensional, time-dependent model of the ion and neutral polar winds was used to study their dynamic evolution during the May 4, 1998 magnetic storm. The simulation tracked the dynamics of five species (O⁺, H⁺, H_s, O_s, and electrons) and covered a 9-h period. During the storm, D_st decreased to −210 nT, Ap reached 300, and K_p was elevated. The IMF B_z component was southward at the start of the storm and for several hours thereafter and then turned northward. However, the magnetospheric energy input to the ionosphere exhibited a 50-min oscillation, with the plasma convection and particle precipitation patterns expanding and contracting in a periodic manner. As a consequence, the ion and neutral polar winds pulsated with an approximate 50-min period. The H⁺ and O⁺ ions displayed cyclic upflows and downflows in the topside ionosphere as well as a highly structured spatial distribution that varied with time. The vertical flux of the neutral H_s atoms was upward at the top of the ionosphere, but the magnitude varied in a cyclic manner in response to the oscillating stormtime energy input. The vertical flux of neutral O_s atoms was downward at the top of the ionosphere and varied significantly with the stormtime energy input. For H⁺, O⁺, and H_s, the maximum total (integrated) vertical flux during the storm was upward at the top of the ionosphere, with values of 8–9×10²⁵ particles/s for H⁺, 2–4×10²⁶ particles/s for O⁺, and 2–3×10²⁷ particles/s for H_s. The corresponding total vertical O_s flux was predominately downward, with only localized areas with positive fluxes.     

Water chemistry of Lake Quilotoa (Ecuador) and assessment of natural hazards

A geochemical survey carried out in November 1993 revealed that Lake Quilotoa was composed by a thin (14 m) oxic epilimnion overlying a 200 m-thick anoxic hypolimnion. Dissolved CO₂ concentrations reached 1000 mg/kg in the lower stratum. Loss of CO₂ from epilimnetic waters, followed by calcite precipitation and a consequent lowering in density, was the apparent cause of the stratification.The Cl, SO₄ and HCO₃ contents of Lake Quilotoa are intermediate between those of acid–SO₄–Cl Crater lakes and those of neutral-HCO₃ Crater lakes, indicating that Lake Quilotoa has a ‘memory’ of the inflow and absorption of HC1- and S-bearing volcanic (magmatic) gases. The Mg/Ca ratios of the lake waters are governed by dissolution of local volcanic rocks or magmas, but K/Na ratios were likely modified by precipitation of alunite, a typical mineral in acid–SO₄–Cl Crater lakes.The constant concentrations of several conservative chemical species from lake surface to lake bottom suggest that physical, chemical and biological processes did not have enough time, after the last overturn, to cause significant changes in the contents of these chemical species. This lapse of time might be relatively large, but it cannot be established on the basis of available data. Besides, the lake may not be close to steady state. Mixing of Lake Quilotoa waters could presently be triggered by either cooling epilimnetic waters by 4°C or providing heat to hypolimnetic waters or by seismic activity.Although Quilotoa lake contains a huge amount of dissolved CO₂ (3×10¹¹ g), at present the risk of a dangerous limnic eruption seems to be nil even though some gas exsolution might occur if deep lake waters were brought to the surface. Carbon dioxide could build up to higher levels in deep waters than at present without any volcanic re-awakening, due to either a large inflow of relatively cool CO₂-rich gases, or possibly a long interval between overturns. Periodical geochemical surveys of Lake Quilotoa are, therefore, recommended.