Precipitation of Fe and Al compounds from the acid mine waters in the dogyae area, Korea: A qualitative measure of equilibrium modeling applicability and neutralization capacity?

To investigate the applicability of equilibrium modeling for the estimation of the chemical changes of acid mine waters, the phases predicted to precipitate by equilibrium calculation were compared with what actually precipitates from the stream and acid mine waters in the Dogyae area, Korea. The computer program MINTEQA2 was used for the equilibrium calculations based on the chemical compositional data of the water samples collected in the study area. XRD, IR, thermal and chemical analyses of the collected precipitates were performed to identify their phases.The results of the identification of the collected precipitates are inconsistent with what the equilibrium calculations predict. The equilibrium calculations indicate that ferrihydrite, FeOHSO₄, gibbsite, and AlOHSO₄ should precipitate from the stream and acid mine waters in the study area. However, the experimental analyses show that only ferrihydrite and Al₄(OH)₁₀SO₄ are the recognizable precipitates on the bottom of the stream and mine drainage channels. Comparing the stability relations among the possible precipitates with the field occurrence of the precipitates in the study area suggests that FeOHSO₄ and AIOHSO₄ are kinetically inhibited to precipitate and metastable ferrihydrite and Al₄(OH)₁₀SO₄ appear in their stability field instead. It indicates that the chemical compositional change of the waters due to the solid phase precipitation in the study area must be interpreted and predicted in terms of the precipitation of not the phases predicted by the equilibrium calculation but the actually identified ones.Assuming that the dissolved species in the aqueous phase are in equilibrium with respect to the currently precipitating solid phases in the study area, the water chemistries are attempted to interpret based on the plot of the theoretically calculated activities of the dissolved species on the stability diagram for the identified precipitates and gibbsite. The plot reveals a few evolution paths of the chemical composition of the acid mine water as the acid generation and neutralization progress. The evolution path producing ferrihydrite and then Al₄(OH)₁₀SO₄ precipitation suggests that the system including acid producing pyrite has lost significant amounts of its neutralizing capacity and thus, become intolerable to the impacts from acid mine water.     

A comparative study of stream water and stream sediment as geochemical exploration media in the Rio Tanama porphyry copper district,Puerto Rico

To test the relative effectiveness of stream water and sediment as geochemical exploration media in the Rio Tanama porphyry copper district of Puerto Rico, we collected and subsequently analyzed samples of water and sediment from 29 sites in the rivers and tributaries of the district. Copper, Mo, Pb, Zn, SO₄^2?, and pH were determined in the waters; Cu, Mo, Pb, and Zn were determined in the sediments. In addition, copper in five partial extractions from the sediments was determined. Geochemical contrast (anomaly-to-background quotient) was the principal criterion by which the effectiveness of the two media and the five extractions were judged.Among the distribution patterns of metals in stream water, that of copper most clearly delineates the known porphyry copper deposits and yields the longest discernable dispersion train. The distribution patterns of Mo, Pb, and Zn in water show little relationship to the known mineralization. The distribution of SO₄^2? in water delineates the copper deposits and also the more extensive pyrite alteration in the district; its recognizable downstream dispersion train is substantially longer than those of the metals, either in water or sediment. Low pH values in small tributaries delineate areas of known sulfide mineralization.The distribution patterns of copper in sediments clearly delineate the known deposits, and the dispersion trains are longer than those of copper in water.The partial determinations of copper related to secondary iron and manganese oxides yield the strongest geochemical contrasts and longest recognizable dispersion trains. Significantly high concentrations of molybdenum in sediments were found at only three sites, all within one-half km downstream of the known copper deposits. The distribution patterns of lead and zinc in sediments are clearly related to the known primary lead-zinc haloes around the copper deposits. The recognizable downstream dispersion trains of lead and zinc are shorter than those of copper.     

Apparent solubilities of schwertmannite and ferrihydrite in natural stream waters polluted by mine drainage

The apparent solubilities of schwertmannite and ferrihydrite were estimated from the H⁺, OH⁻, Fe³⁺, and SO₄²⁻ activities of the natural stream waters in Korea and mine drainage in Ohio, USA. Both chemical composition of the stream waters and the mineralogy of the precipitates were determined for samples from two streams polluted by coal mine drainage. This study combines these new results with previous data from Ohio, USA to redetermine solubilities. The activities of the dissolved species necessary for the solubility determinations were calculated from the chemical compositions of the waters with the WATEQ4F computer code.Laboratory analyses of precipitates indicated that the main minerals present in Imgok and Osheep creek were schwertmannite and ferrihydrite, respectively. The schwertmannite from Imgok creek had a variable chemical formula of Fe₈O₈(OH)_8−2x(SO₄)_x· nH₂O, where 1.74 ≤ x ≤ 1.86 and 8.17 ≤ n ≤ 8.62. The chemical formula of ferrihydrite was Fe₂O₃· 1.6H₂O. With known mineralogy of the precipitates from each stream, the activities of H⁺, OH⁻, Fe³⁺, and SO₄²⁻ in the waters were plotted on logarithmic activity-activity diagrams to determine apparent solubilities of schwertmannite and ferrihydrite. The best estimate for the logarithm of the solubility product of schwertmannite, logK_s, was 10.5 ± 2.5 around 15°C. This value of logK_s constrains the logarithm of the solubility product of ferrihydrite, logK_f, to be 4.3 ± 0.5 to maintain the stability boundary with schwertmannite observed in natural waters.     

Hydrogeochemistry in the Vouga River basin (central Portugal): Pollution and chemical weathering

To quantify and explain the contributions by pollution and chemical weathering to their composition, we studied the chemistries of springs and surface waters in the mountainous part of the Vouga River basin. Water samples were collected during a number of consecutive summer campaigns. Recharge rates were derived from monitored discharge rates within the basin. Very large contributions by meteoric, agricultural and domestic sources to the water chemistries were found, identified by the chloride, sulfate and nitrate concentrations: on average only 1/4 to 1/3 of the solutes could be attributed to chemical weathering. Two petrologic units characterize the river basin: granites and metasediments. The waters collected within metasediment units are distinct from those in granite terrain by a higher magnesium concentration. On that basis, it could be estimated that the Rio Vouga, when leaving the mountainous part of the basin, has for some 2/5 a signature determined by chemical weathering in the metasediments. The dominant primary minerals subject to chemical weathering are plagioclase (Pl) and biotite (in granite) or Pl and chlorite (in metasediment). Kaolinite, gibbsite and vermiculite are the major weathering products where annual precipitation (P) > 1000 mm y⁻¹, and kaolinite, vermiculite and smectite where P was lower. Using an algorithm based on the ratio of dissolved silica to bicarbonate, the contributions of chemical weathering of primary minerals could be unraveled. The results show that in granite the export rate (as mol ha⁻¹ y⁻¹ wt%mineral⁻¹) of oligoclase (Pl with An_10–30) was 5.0 ± 2.6 and of biotite 3.2 ± 2.6, while in metasediment these rates for albite (Pl with An_0–10) are 16.5 ± 8.9 and for chlorite are 0.5 ± 0.5. The observed decrease of dissolved silica in surface waters relative to springs was ascribed to (summer) uptake by aquatic biota.     

The hydrogeochemistry of the Lake Waco drainage basin,Texas

The origin of surface water chemistry in highly impacted drainage basins must be investigated on a drainage-basin scale if the causes of the pollution are to be elucidated. This study characterizes and deciphers the surface water chemistry of a nutrient polluted river system in central Texas. Four tributaries of the Lake Waco reservoir were chemically characterized temporally and spatially in order to gain a complete understanding of the nature and origin of dissolved solids being transported into the lake. Temporal chemical variations measured at the base of each of the drainage basins are repetitive and seasonal. The most periodic and well-defined variation is exhibited by nitrate concentrations although many of the other solutes show seasonal changes as well. These temporal chemical changes are controlled by seasonal precipitation. During rainy seasons, the shallow aquifer is recharged resulting in stream discharge that is high in nitrate, calcium, and bicarbonate. When the shallow flow system is depleted in the summer, stream waters are dominated by deeper groundwater and become rich in sodium. Spatial variations in the chemistry of South Bosque surface waters were characterized using the snapshot technique. The spatial distribution of nitrate in surface waters is controlled by fertilizer application to row crops and the location of a munitions factory. The concentrations of naturally derived solutes such as Ca⁺, Na⁺, Cl^–, and SO₄^–2are controlled by underlying lithologies.     

Geothermometry applications for the Balıkesir thermal waters,Turkey

In this study, reservoir temperatures of Balıkesir geothermal waters in northwestern Turkey are estimated with various geochemical models. The geothermal fluids in the region are represented by Na–SO₄, Na–HCO₃ and Ca–HCO₃ type waters with discharge temperatures up to 98°C. It was determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Balıkesir thermal waters studied by means of Na–K–Mg–Ca diagram, mineral saturation calculations and activity diagrams in the system composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–H₂O phases approximate a reservoir temperature of about 120°C. Most of the waters are found to be equilibrated with calcite, chalcedony ± quartz and muscovite at predicted temperature ranges, similar to those calculated from the chemical geothermometers.     

Seasonal variation in major ion chemistry of a tropical mountain river,the southern Western Ghats,Kerala, India

A comprehensive and systematic study to understand various geochemical processes as well as process drivers controlling the water quality and patterns of the hydrochemical composition of river water in Muthirapuzha River Basin, MRB (a major tributary of Periyar, the longest river in Kerala, India), was carried out during various seasons, such as monsoon, post-monsoon and pre-monsoon of 2007–2008, based on the data collected at 15 monitoring stations (i.e., 15 × 3 = 45 samples). Ca²⁺ and Mg²⁺ dominate the cations, while Cl^? followed by HCO₃ ^? dominates the anions. In general, major ion chemistry of MRB is jointly controlled by weathering of silicate and carbonate rocks, which is confirmed by relatively larger Ca²⁺ + Mg²⁺/Na⁺ + K⁺ ratios as well as Ca²⁺/Na⁺ vs. Mg²⁺/Na⁺ and Ca²⁺/Na⁺ vs. HCO₃ ^?/Na⁺ scatter plots. The relationship between Cl^? and Na⁺ implies stronger contributions of anthropogenic activities modifying the hydrochemical composition, irrespective of seasons. The water types emerged from this study are transitional waters or waters that changed their chemical character by mixing with waters of geochemically different ionic signatures. However, various ionic ratios, hydrochemical plots and graphical diagrams suggest seasonality over the hydrochemical composition, which is solely controlled by the rainfall pattern. Relatively higher pCO₂ indicates the disequilibrium existing in natural waterbodies vis-à-vis the atmosphere, which is an outcome of both the contribution of groundwater to stream discharge and anthropogenic activities. Hence, continuous monitoring of hydrochemical composition of mountain rivers is essential in the context of climate change, which has serious implications on tropical mountain fluvial-hydro systems.     

Interpretative matrices approach to ranking lake sub-basin pollution potential: an applied study in Brazil

In 2005 a Cylindrospermopsis raciborskii bloom occurred in the Rio Verde Lake Basin (Brazil). To address this concern, a field analysis was performed to measure physicochemical variables and flows in 14 sub-basins, between 2008 and 2009. Measurements of mean total P (0.039 mg/L ± 0.018 mean SD), mean total Kjeldahl N (0.260 mg/L ± 0.226 mean SD), and mean BOD (1.2 mg/L ± 0.4 mean SD) concentrations were low in most streams, while COD reached a high of 27.1 mg/L (±4.9 mean SD). One tributary was responsible for 85 % of TP load, 77.1 % of TKN load, 78 % of t-BOD load, and 79 % of t-COD load. These concentrations and loads were used to develop the pollution potential assessment matrix (2PAM), which considered three different perspectives: stream water quality, reservoir ecosystem equilibrium, and sub-basin management. Each factor (TP, TKN, BOD and COD) was weighted based on concentration, total load and unit-area load. Pollution potential differed depending on which perspective was considered. The matrix developed, 2PAM, provides a new way to analyze concentrations and loads, enabling basin managers to prioritize action plans according to desired use within the basin.     

Ferromanganese carbonate metasediments of the Sob area,Polar Urals: Bedding conditions,composition, and genesis

The paper presents the results of study of ferromanganese carbonate rocks in the Sob area (Polar Urals), which is located between the Rai-Iz massif and the Seida–Labytnangi Railway branch. These rocks represent low-metamorphosed sedimentary rocks confined to the Devonian carbonaceous siliceous and clayey–siliceous shales. In terms of ratio of the major minerals, ferromanganese rocks can be divided into three varieties composed of the following minerals: (1) siderite, rhodochrosite, chamosite, quartz, ± kutnahorite, ± calcite, ± magnetite, ± pyrite, ± clinochlore, ± stilpnomelane; (2) spessartite, rhodochrosite, and quartz, ± hematite, ± chamosite; (3) rhodochrosite, spessartite, pyroxmanite, quartz ± tephroite, ± fridelite, ± clinochlore, ± pyrophanite, ± pyrite. In all varieties, the major concentrators of Mn and Fe are carbonates (rhodochrosite, siderite, kutnahorite, Mn-calcite) and chlorite group minerals (clinochlore, chamosite). The chemical composition of rocks is dominated by Si, Fe, Mn, carbon dioxide, and water (L.O.I.): total SiO₂ + Fe₂O ₃ ^tot + MnO + L.O.I. = 85.6?98.4 wt %. The content of Fe and Mn varies from 9.3 to 55.6 wt % (Fe₂O ₃ ^tot + MnO). The Mn/Fe ratio varies from 0.2 to 55.3. In terms of the aluminum module Al_M = Al/(Al + Mn + Fe), the major portion of studied samples corresponds to metalliferous sediments. The δ¹³C_carb range (–30.4 to–11.9‰ PDB) corresponds to authigenic carbonates formed with carbon dioxide released during the microbial oxidation of organic matter in sediments at the dia- and/or catagenetic stage. Ferromanganese sediments were likely deposited in relatively closed seafloor zones (basin-traps) characterized by periodic stagnation. Fe and Mn could be delivered from various sources: input by diverse hydrothermal solutions, silt waters in the course of diagenesis, river discharges, and others. The diagenetic delivery of metals seems to be most plausible. Mn was concentrated during the stagnation of bottom water in basin-traps. Interruption of stagnation promoted the precipitation of Mn. The presence of organic matter fostered a reductive pattern of postsedimentary transformations of metalliferous sediments. Fe and Mn were accumulated initially in the oxide form. During the diagenesis, manganese and iron oxides reacted with organic matter to make up carbonates. Relative to manganese carbonates, iron carbonates were formed under more reductive settings and higher concentrations of carbon dioxide in the interstitial solution. Crystallization of manganese and iron silicates began already at early stages of lithogenesis and ended during the regional metamorphism of metalliferous sediments.     

A chemical survey of the Mississippi estuary

A “snap shot” survey of the Mississippi estuary was made during a period of low river discharge, when the estuarine mixing zone was within the deltaic channels. Concentrations of H⁺, Ca²⁺, inorganic phosphorus and inorganic carbon suggest that the waters of the river and the low salinity (<5‰) portion of the estuary are near saturation with respect to calcite and sedimentary calcium phosphate. An input of oxidized nitrogen species and N₂O was observed in the estuary between 0 and 4‰ salinity. The concentrations of dissolved NH₄ ⁺ and O₂, over most of the estuary, appeared to be influenced by decomposition of terrestrial organic matter in bottom sediments. The estuarine bottom also appears to be a source of CH₄ which has been suggested to originate from petroleum shipping and refining operations. Estuarine mixing with offshore Gulf waters was the dominant influence on distributions of dissolved species over most of the estuary (i.e., from salinities >5‰). The phytoplankton abundance (measured as chlorophylla) increased as the depth of the mixed layer decreased in a manner consistent with that expected for a light-limited ecosystem. Fluxes of NO₃ ^?+NO₂ ^? and soluble inorganic phosphorus to the Gulf of Mexico were estimated to be 3.4±0.2×10³ g N s^?1 and 1.9±0.2 g P s^?1 respectively, at the time of this study.     

<Superscript>238</Superscript>U and <Superscript>235</Superscript>U isotope fractionation upon oxidation of uranium-bearing rocks by fracture waters

The variations in ²³⁸U/²³⁵U values accompanying mobilization of U by fracture waters from uranium-bearing rocks, in which U occurs as a fine impregnation of oxides and silicates, were studied by the high-precision (±0.07‰) MC–ICP–MS method. Transition of U into the aqueous phase in the oxidized state U(VI) is accompanied by its isotope fractionation with enrichment of dissolved U(VI) in the heavy isotope ²³⁸U up to 0.32‰ in relation to the composition of the solid phases. According to the sign, this effect is consistent with the tendency of the behavior of ²³⁸U and ²³⁵U upon interaction of river waters with rocks of the catchment areas [11] and with the effect observed during oxidation of uraninite by the oxygen-bearing NaHCO₃ solution [12].     

Geochemical and Sr-isotopic characteristics of stream and spring waters from small-forested catchments at Seto,central Japan

Hydrogeochemical processes controlling surface water chemistry were examined in five small (<1.5 km ²) forested catchments that have contrasting bedrock lithologies of granite, and conglomerate, and are distributed in the southeast of Seto district, central Japan. Watersheds developed on these two bedrocks differ in their ability to neutralize atmospheric acid (pH ~4.5) deposition. The study was conducted to (1) characterize the hydrogeochemical processes controlling surface water chemistry, and (2) to elucidate acidification of spring and stream waters using data from three sampling campaigns conducted from August to October 2000. Stream and spring water solutes fall into two general groups according to concentration: alkaline, relatively high pH (5.2–7.7) and high cation concentrations (HCO ₃ ^-, Cl ^-, base cations), and dilute, low pH (4.2–5.5) waters. Concentrations of trace metals (Al, Ba, Sr) showed a strong negative correlation with pH, suggesting the mobility of these metals in the dissolved load of catchments underlain by Tokai conglomerate. The strontium isotope ratio ( ⁸⁷Sr/ ⁸⁶Sr) of rock and soil, plant, precipitation, and surface water samples was used to identify different reservoirs within the ecosystem. Low Si concentrations in stream and spring waters from the conglomerate area, with a relatively high pool of SiO ₂, >90 (wt%), suggest slow chemical weathering. The dissolved solute concentrations are generally of similar magnitude in stream waters within the catchments of similar bedrock lithology. The high inverse correlation ( r ²=0.72) between pH and SO ₄ ^– concentrations and the high positive correlation ( r ² =0.90) between Ba and SO ₄ ^– concentrations in waters draining Tokai conglomerate suggest that barite (BaSO ₄) is being dissolved in an acidic environment. The three catchments were identified as being sensitive to acidic deposition because the bedrock conglomerate provided little capacity to buffer acidic inputs. The soils from the granite area have a high cation-exchange capacity (CEC an average of 868 µmol/kg), and are nearly ten times greater than the soils from the conglomerate area. Because ion exchange, besides weathering, is the main source that counteracts soil acidification, the sensitivity to further acidification may increase.     

The partitioning of copper among selected phases of geologic media of two porphyry copper districts, Puerto Rico

In experiments designed to determine the manner in which copper is partitioned among selected phases that constitute geologic media, we have applied the five-step sequential extraction procedure of Chao and Theobald to the analysis of drill core, soils, and stream sediments of the Rio Vivi and Rio Tanama porphyry copper districts of Puerto Rico. The extraction procedure affords a convenient means of determining the trace-metal content of the following fractions: (1) Mn oxides and “reactive” Fe oxides; (2) “amorphous” Fe oxides; (3) “crystalline” Fe oxides; (4) sulfides and magnetite; and (5) silicates. An additional extraction between steps (1) and (2) was performed to determine organic-related copper in stream sediments.The experimental results indicate that apportionment of copper among phases constituting geologic media is a function of geochemical environment. Distinctive partitioning patterns were derived from the analysis of drill core from each of three geochemical zones: (a) the supergene zone of oxidation; (b) the supergene zone of enrichment; and (c) the hypogene zone; and similarly, from the analysis of; (d) soils on a weakly leached capping; (e) soils on a strongly leached capping; and (f) active stream sediment.The experimental results also show that geochemical contrasts (anomaly-to-background ratios) vary widely among the five fractions of each sampling medium investigated, and that at least one fraction of each medium provides substantially stronger contrast than does the bulk medium. Fraction (1) provides optimal contrast for stream sediments of the district; fraction (2) provides optimal contrast for soils on a weakly leached capping; fraction (3) provides optimal contrast for soils on a strongly leached capping.Selective extraction procedures appear to have important applications to the orientation and interpretive stages of geochemical exploration. Further investigation and testing of a similar nature are recommended.     

Weathering and Geochemical Processes Controlling Solute Acquisition in Ganga Headwater–Bhagirathi River, Garhwal Himalaya, India

Water and suspended sediment samples were collected along a longitudinal transect of the Bhagirathi – a headwater stream of the river Ganga, during the premonsoon and postmonsoon seasons, in order to assess the solute acquisition processes and sediment transfer in a high elevation river basin. Study results show that surface waters were dominated by HCO₃ and SO₄ in anionic abundance and Ca in cationic concentrations. A high concentration of sulphate in the source region indicates oxidative weathering of sulphide bearing minerals in the drainage basin. The combination of high concentrations of calcium, bicarbonate and sulphate in river water suggests that coupled reaction involving sulphide oxidation and carbonate dissolution are mainly controlling the solute acquisition processes in the drainage basin. The sediment transfer reveals that glacial weathering and erosion is the major influence on sediment production and transfer. The seasonal and spatial variation in ionic concentration, in general, is related to discharge and lithology. The sediment mineralogy and water mineral equilibrium indicate that water composition is in equilibrium with kaolinite. The river Bhagirathi annually delivers 0.74 M.tons of dissolved and 7.88 M.tons of suspended load to the river Ganga at Devprayag. The chemical and physical denudation rate of the Bhagirathi is 95 and 1010 tons/km²/yr, higher than the Indian and global average.     

Understanding the controls on sediment-P interactions and dynamics along a non-tidal river system in a rural–urban catchment: The River Nene

The release of Phosphorus (P) from river sediments has been identified as a contributing factor to waters failing the criteria for ‘Good Ecological Status’ under the EU Water Framework Directive (WFD). To identify the contribution of sediment-P to river systems, an understanding of the factors that influence its distribution within the entire non-tidal system is required. Thus the aims of this work were to examine the (i) total (P_Total) and labile (P_Labile) concentrations in sediment, (ii) the sequestration processes and (iii) the interactions between sediment P and the river water in the six non-tidal water bodies of the River Nene, U.K. Collection of sediments followed a long period of flooding and high stream flow. In each water body, five cores were extracted and homogenised for analysis with an additional core being taken and sampled by depth increments. Comparing the distribution of sediment particle size and P_Total data with soil catchment geochemical survey data, large increases in P_Total were identified in sediments from water body 4–6, where median concentrations of P_Total in the sediment (3603 mg kg⁻¹) were up to double those of the catchment soils. A large proportion of this increase may be related to in-stream sorption of P, particularly from sewage treatment facilities where the catchment becomes more urbanised after water body 3. A linear correlation (r = 0.8) between soluble reactive phosphate (SRP) and Boron in the sampled river waters was found suggesting increased STW input in water bodies 4–6.P_Labile concentrations in homogenised cores were up to 100 mg kg⁻¹ PO₄–P (generally < 2% of P_Total) and showed a general increase with distance from the headwaters. A general increase in Equilibrium Phosphate Concentrations (EPC₀) from an average of 0.9–∼1.7 μm L⁻¹ was found between water bodies 1–3 and 4–6. Fixation within oxalate extractable phases (Al, Fe and Mn) accounted for ∼90% of P binding in water bodies 4–6, but only between 31 and 74% in water bodies 1–3. Statistical models predicting P_Total (R² = 0.78), oxalate extractable P (R² = 0.78) and Olsen P (R² = 0.73) concentrations in river sediments identified Mn oxy-hydroxides (MnO_x) as a strong predictive variable along with the location within the river system. It is suggested that MnO_x within model predictions is identifying a pool of mixed Fe–Mn oxy-hydroxides (MnO_x–FeOOH) or Fe oxy-hydroxide (FeOOH) from the wider Fe_Oxalate pool that are particularly effective at sorbing and fixing P. The findings demonstrate how sediment and P may accumulate along a 100 km non-tidal river system, the extent to which a range of processes can fix P within mineral phases and how natural flooding processes may flush sediment from the river channel. The processes identified in this study are likely to be applicable to similar river systems over their non-tidal water bodies in eastern England.     

Liquid immiscibility in the system NaF–H<Subscript>2</Subscript>O and microlite solubility at 800°C

The NaF effect on microlite solubility at 800°C and 170, 200, and 230 MPa is studied experimentally. The immiscibility boundaries and compositions of fluid phases L₁ and L₂ are defined in the system NaF–H₂O at 800°C. It is established that microlite solubility increase in the L₁ phase, as compared with a homogeneous solution, is explained by the appearance in the L₁ phase of “free” HF in an amount of 0.025 ± 0.003 mol kg^–1 H₂O. The model of “acidification” L₁ and “alkalizing” L₂ is supposed.     

Transportation and evolution of trace element bearing phases in stream sediments in a mining – Influenced basin (Upper Isle River,France)

Arsenic-bearing stream sediments enter the Upper Isle River, an Au mining-influenced basin (France), by the discharge of mining sites, tailings runoff and weathering of mineralized veins in granites and gneiss. Some fresh ochreous As-rich deposits on the river banks and in floodplains are identified as additional As-rich point sources (As between 0.07 and 6.5 wt.%). The <63 μm fraction of stream sediments contains elevated As bulk concentrations, ranging from 160 to 890 mg/kg, compared to the geochemical background (70 mg/kg on average). It is also enriched in Cd, Hg and W. Spatial variations of these trace elements show 3 significant increases corresponding to the 3 drained mining districts. They decrease down river but are still enriched 30 km downstream of the mining districts due to downstream transportation. Three types of trace element-bearing phases have been identified as: (i) detrital primary sulfides, with high in situ As percentages (up to 43.7 wt.%). They also carry significant amounts of W according to the differences in chemical compositions of the total and light <63 μm fractions. These sulfide particles do not show any sign of alteration in the oxygenated stream sediments; (ii) Secondary Fe–Mn oxyhydroxides,some with very high in situ As₂O₅ concentrations (up to 59.8 wt.%) and with about 40% of the total Cd composition. They occur as fresh precipitates in the river banks and floodplains and as discrete particles in stream sediments and (iii) Al–Si fine-grained phases. Their major element composition is highly variable with in situ As₂O₅ concentrations ranging between 430 and 5020 mg/kg. This type of solid phase is also the major carrier of Hg.     

Carbon dioxide emissions from the Three Gorges Reservoir,China

Carbon dioxide (CO₂) emission from the river-type reservoir is an hotspot of carbon cycle within inland waters. However, related studies on the different types of reservoirs are still inadequate. Therefore, we sampled the Three Gorges Reservoir (TGR), a typical river-type reservoir having both river and lake characteristics, using an online system (HydroCTM/CO₂) and YSI-6600v2 meter to determine the partial pressure of carbon dioxide (pCO₂) and physical chemical parameters in 2013. The results showed that the CO₂ flux from the mainstream ranged from 26.1 to 92.2 mg CO₂/m² h with average CO₂ fluxes of 50.0 mg/m² h. The CO₂ fluxes from the tributary ranged from ?10.91 to 53.95 mg CO₂/m² h with area-weighted average CO₂ fluxes of 11.4 mg/m² h. The main stream emits CO₂ to the atmosphere the whole year; however, the surface water of the tributary can sometimes act as a sink of CO₂ for the atmosphere. As the operation of the TGR, the tributary became more favorable to photosynthetic uptake of CO₂ especially in summer. The total CO₂ flux was estimated to be 0.34 and 0.03 Tg CO₂/year from the mainstream and the tributaries, respectively. Our emission rates are lower than previous estimates, but they are in agreement with the average CO₂ flux from temperate reservoirs estimated by Barros et al. (Nat Geosci 4(9):593–596, 2011).     

Hydrogeochemical evaluation of fractured Limestone aquifer by applying a geochemical model in eastern Nile Valley,Egypt

Rock water interactions play an important role in the flow of groundwater. Groundwater samples were collected from deep production wells with depths ranging from 120 to 230 m. Complete chemical analysis of 40 groundwater samples was collected from the fractured limestone aquifer including major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and major anions (Cl^?, SO₄ ^2?, HCO₃ ^?, CO₃ ^2?). A geochemical modeling (NETPATH Software) was applied for environmental simulate net geochemical mass-balance reactions between initial and final waters along a hydrologic flow path. This program simulates selected evolutionary waters for every possible combination of the plausible phases that account for the composition of a selected set of chemical constraints in the system. The groundwater of the Eocene aquifer mainly belongs to fairly fresh water with salinity contents ranging from 228 to 3595 ppm. The measured groundwater levels range between 8 and 25 m near the river Nile to the limestone plateau (eastwards). Consequently, groundwater flows from east to westward toward the river Nile. Groundwater aquifer in the study area is mainly composed of fractured limestone; the saturated states of the PCO₂, calcite, aragonite, dolomite, siderite, gypsum, anhydrite, hematite, and goethite in addition to H₂ gas were estimated. The undersaturated state of carbon dioxide reflects closed conditions and very low probability of recent recharge, and it reveals also the high tendency of water to precipitates carbonate species. Undersaturation by carbonate minerals is only restricted to some pockets distributed on the different places of the aquifer in the study area. The majority of groundwater samples of Eocene aquifer in the study area indicated that groundwater is not suitable for irrigation with treatment and requires good drainage.     

A study of the pollution of the Aries River (Romania) using capillary electrophoresis as analytical technique

 This paper examines two issues, the extensive pollution occurring in the Aries River, NW Romania, as a result of unchecked discharge of mining effluents into the river system, and the suitability of capillary electrophoresis (CE) as an analytical method for investigations into water chemistry. The results confirm the first objective by providing details on the pollution of the Aries River and its geochemical system and demonstrate the usefulness of CE. In its upper reaches, the river system is characterized by high contents of SO₄ ^2– as a direct result of acid mine effluents and the oxidation of sulphide minerals on mine dumps as well as inflows from settling ponds. Although continuous dilution by natural branch waters and natural water-rock interaction reduces the pollution to some extend, the total level of SO₄ ^2– remains above European averages. The waters of the Aries River, by comparison, contain contents of Cu²⁺ and Zn²⁺ up to 100 times higher than those of unpolluted river water. Received: 1 November 1999 · Accepted: 3 April 2000