Origin and evolution of two contrasting thermal groundwaters (CO2-rich and alkaline) in the Jungwon area,South Korea: Hydrochemical and isotopic evidence

In the Jungwon area, South Korea, two contrasting types of deep thermal groundwater (around 20–33 °C) occur together in granite. Compared to shallow groundwater and surface water, thermal groundwaters have significantly lower δ¹⁸O and δD values (> 1‰ lower in δ¹⁸O) and negligible tritium content (mostly < 2 TU), suggesting a relatively high age of these waters (at least pre-thermonuclear period) and relatively long subsurface circulation. However, the hydrochemical evolution yielded two distinct water types. CO₂-rich water (P_CO2 = 0.1 to 2 atm) is characterized by lower pH (5.7–6.4) and higher TDS content (up to 3300 mg/L), whereas alkaline water (P_CO2 = 10^− 4.1–10^− 4.6 atm) has higher pH (9.1–9.5) and lower TDS (< 254 mg/L). Carbon isotope data indicate that the CO₂-rich water is influenced by a local supply of deep CO₂ (potentially, magmatic), which enhanced dissolution of silicate minerals in surrounding rocks and resulted in elevated concentrations of Ca²⁺, Na⁺, Mg²⁺, K⁺, HCO₃⁻ and silica under lower pH conditions. In contrast, the evolution of the alkaline water was characterized by a lesser degree of water–rock (granite) interaction under the negligible inflow of CO₂. The application of chemical thermometers indicates that the alkaline water represents partially equilibrated waters coming from a geothermal reservoir with a temperature of about 40 °C, while the immature characteristics of the CO₂-rich water resulted from the input of CO₂ in Na–HCO₃ waters and subsequent rock leaching.     

Hydrogeochemistry of the Simav geothermal field, western Anatolia, Turkey

Thermal waters hosted by Menderes metamorphic rocks emerge along fault lineaments in the Simav geothermal area. Thermal springs and drilled wells are located in the Eynal, Çitgöl and Na a locations, which are part of the Simav geothermal field. Studies were carried out to obtain the main chemical and physical characteristics of thermal waters. These waters are used for heating of residences and greenhouses and for balneological purposes. Bottom temperatures of the drilled wells reach 163°C with total dissolved solids around 2225 mg/kg. Surface temperatures of thermal springs vary between 51°C and 90°C. All the thermal waters belong to Na–HCO₃–SO₄ facies. The cold groundwaters are Ca–Mg–HCO₃ type. Dissolution of host rock and ion-exchange reactions in the reservoir of the geothermal system shift the Ca–Mg–HCO₃ type cold groundwaters to the Na–HCO₃–SO₄ type thermal waters. Thermal waters are oversaturated at discharge temperatures for aragonite, calcite, quartz, chalcedony, magnesite and dolomite minerals giving rise to a carbonate-rich scale. Gypsum and anhydrite minerals are undersaturated with all of the thermal waters. Boiling during ascent of the thermal fluids produces steam and liquid waters resulting in an increase of the concentrations of the constituents in discharge waters. Steam fraction, y, of the thermal waters of which temperatures are above 100°C is between 0.075 and 0.119. Reservoir pH is much lower than pH measured in the liquid phase separated at atmospheric conditions, since the latter experienced heavy loss of acid gases, mainly CO₂. Assessment of the various empirical chemical geothermometers and geochemical modelling suggest that reservoir temperatures vary between 175°C and 200°C.     

Volatile emissions and gas geochemistry of Hot Spring Basin,Yellowstone National Park,USA

We characterize and quantify volatile emissions at Hot Spring Basin (HSB), a large acid-sulfate region that lies just outside the northeastern edge of the 640 ka Yellowstone Caldera. Relative to other thermal areas in Yellowstone, HSB gases are rich in He and H₂, and mildly enriched in CH₄ and H₂S. Gas compositions are consistent with boiling directly off a deep geothermal liquid at depth as it migrates toward the surface. This fluid, and the gases evolved from it, carries geochemical signatures of magmatic volatiles and water–rock reactions with multiple crustal sources, including limestones or quartz-rich sediments with low K/U (or ^40?Ar/^4?He). Variations in gas chemistry across the region reflect reservoir heterogeneity and variable degrees of boiling. Gas-geothermometer temperatures approach 300 °C and suggest that the reservoir feeding HSB is one of the hottest at Yellowstone. Diffuse CO₂ flux in the western basin of HSB, as measured by accumulation-chamber methods, is similar in magnitude to other acid-sulfate areas of Yellowstone and is well correlated to shallow soil temperatures. The extrapolation of diffuse CO₂ fluxes across all the thermal/altered area suggests that 410 ± 140 t d^− 1 CO₂ are emitted at HSB (vent emissions not included). Diffuse fluxes of H₂S were measured in Yellowstone for the first time and likely exceed 2.4 t d^− 1 at HSB. Comparing estimates of the total estimated diffuse H₂S emission to the amount of sulfur as SO₄²⁻ in streams indicates ~ 50% of the original H₂S in the gas emission is lost into shallow groundwater, precipitated as native sulfur, or vented through fumaroles. We estimate the heat output of HSB as ~ 140–370 MW using CO₂ as a tracer for steam condensate, but not including the contribution from fumaroles and hydrothermal vents. Overall, the diffuse heat and volatile fluxes of HSB are as great as some active volcanoes, but they are a small fraction (1–3% for CO₂, 2–8% for heat) of that estimated for the entire Yellowstone system.     

Geochemistry of the thermal springs and fumaroles of Basse-Terre Island,Guadeloupe, Lesser Antilles

 The purpose of this work was to study jointly the volcanic-hydrothermal system of the high-risk volcano La Soufrière, in the southern part of Basse-Terre, and the geothermal area of Bouillante, on its western coast, to derive an all-embracing and coherent conceptual geochemical model that provides the necessary basis for adequate volcanic surveillance and further geothermal exploration. The active andesitic dome of La Soufrière has erupted eight times since 1660, most recently in 1976–1977. All these historic eruptions have been phreatic. High-salinity, Na–Cl geothermal liquids circulate in the Bouillante geothermal reservoir, at temperatures close to 250  °C. These Na–Cl solutions rise toward the surface, undergo boiling and mixing with groundwater and/or seawater, and feed most Na–Cl thermal springs in the central Bouillante area. The Na–Cl thermal springs are surrounded by Na–HCO₃ thermal springs and by the Na–Cl thermal spring of Anse à la Barque (a groundwater slightly mixed with seawater), which are all heated through conductive transfer. The two main fumarolic fields of La Soufrière area discharge vapors formed through boiling of hydrothermal aqueous solutions at temperatures of 190–215  °C below the "Ty" fault area and close to 260  °C below the dome summit. The boiling liquid producing the vapors of the Ty fault area has δD and δ¹⁸O values relatively similar to those of the Na–Cl liquids of the Bouillante geothermal reservoir, whereas the liquid originating the vapors of the summit fumaroles is strongly enriched in ¹⁸O, due to input of magmatic fluids from below. This process is also responsible for the paucity of CH₄ in the fumaroles. The thermal features around La Soufrière dome include: (a) Ca–SO₄ springs, produced through absorption of hydrothermal vapors in shallow groundwaters; (b) conductively heated, Ca–Na–HCO₃ springs; and (c) two Ca–Na–Cl springs produced through mixing of shallow Ca–SO₄ waters and deep Na–Cl hydrothermal liquids. The geographical distribution of the different thermal features of La Soufrière area indicates the presence of: (a) a central zone dominated by the ascent of steam, which either discharges at the surface in the fumarolic fields or is absorbed in shallow groundwaters; and (b) an outer zone, where the shallow groundwaters are heated through conduction or addition of Na–Cl liquids coming from hydrothermal aquifer(s). Received: 9 November 1998 / Accepted: 15 July 1999     

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.     

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).     

Rapid physically driven inversion of the air–sea ice CO2 flux in the seasonal landfast ice off Barrow,Alaska after onset of surface melt

The air–sea ice CO₂ flux was measured over landfast sea ice in the Chukchi Sea, off Barrow, Alaska in late May 2008 with a chamber technique. The ice cover transitioned from a cold early spring to a warm late spring state, with an increase in air temperature and incipient surface melt. During melt, brine salinity and brine dissolved inorganic carbon concentration (DIC) decreased from 67.3 to 18.7 and 3977.6 to 1163.5 μmol kg⁻¹, respectively. In contrast, the salinity and DIC of under-ice water at depths of 3 and 5 m below the ice surface remained almost constant with average values of 32.4±0.3 (standard deviation) and 2163.1±16.8 μmol kg⁻¹, respectively. The air–sea ice CO₂ flux decreased from +0.7 to −1.0 mmol m⁻² day⁻¹ (where a positive value indicates CO₂ being released to the atmosphere from the ice surface). During this early to late spring transition, brought on by surface melt, sea ice shifted from a source to a sink for atmospheric CO₂, with a rapid decrease of brine DIC likely associated with a decrease in the partial pressure of CO₂ of brine from a supersaturated to an undersaturated state compared to the atmosphere. Formation of superimposed ice coincident with melt was not sufficient to shut down ice–air gas exchange.     

柴达本盆地沙下盐湖的卤水化学及矿物沉积特征——以察尔汗盐湖区北部外围地带为例

对柴达木盆地察尔汗盐湖区外围沙下盐湖的卤水及沉积进行了综合研究。沙下盐湖卤水化学组成与地表径流和开放性盐湖卤水之间存在明显的差异性,具有高Na⁺+Cl^-、低Mg²⁺+Ca²⁺+SO₄^2-、贫K⁺+CO₃^2-+HCO₃^-等特征。沙下盐湖析盐层位含有新生矿物并夹带碎屑矿物,其盐类矿物组合为:石盐+羟氯镁铝石+光卤石。25℃等温蒸发相图表明,其卤水演化方向往光卤石析出区迁移,在穿越上覆盖层通道中卤水发生的物理化学反应与独特的沉积特征,可以作为继续寻找沙下盐湖的指导。     

Fumarole compositions and mercury emissions from the Tatun Volcanic Field,Taiwan: Results from multi-component gas analyser,portable mercury spectrometer and direct sampling techniques

Gas emissions from Tatun volcanic group, northern Taiwan, were studied for the first time using a multi-component gas analyser system (Multi-GAS) in combination with Giggenbach flask methods at fumaroles and mud pools at Da-you-keng (DYK) and Geng-tze-ping (GZP). CO₂/S molar ratios observed at DYK ranged from 3–17, similar ratios were observed using a Multi-GAS sensor box of 8–16. SO₂ at GZP was low, higher concentrations were observed at DYK where SO₂/H₂S ratios were close to 1 for both methods. A lower CO₂/H₂S ratio was measured via Giggenbach flask sampling (7.2) than was found in the plume using the gas sensor at GZP (9.2). This may reflect rapid oxidation of H₂S as it mixes with background air. Gaseous elemental mercury (GEM) levels were observed in the fumarole gases using a portable mercury spectrometer. These are the first such measurements of mercury at Tatun. Mean GEM concentrations in the fumarole plumes were ∼ 20 ng m^− 3, with much higher concentrations observed close to the ground (mean [GEM] 130 and 290 ng m^− 3 at DYK and GZP, respectively). The GEM in the fumarole plume was elevated above concentrations in industrial/urban air in northern Taiwan and the increase in GEM observed when the instrument was lowered suggests high levels of mercury are present in the surrounding ground surface. The GEM/CO₂ (10^− 8) and GEM/S (10^− 6) ratios observed in the fumarole gases were comparable to those observed at other low-temperature fumaroles. Combining the Hg/CO₂ ratio with a previous CO₂ flux value for the area, the annual GEM flux from the Tatun field is estimated as 5–50 kg/year.     

Chemical geothermometry and fluid–mineral equilibria for the Ömer–Gecek thermal waters, Afyon area, Turkey

Thermal waters of the Ömer–Gecek geothermal field, Turkey, with temperatures ranging from 32 to 92°C vary in chemical composition and TDS contents. They are generally enriched in Na–Cl–HCO₃ and suggest deep water circulation. Silica and cation geothermometers applied to the Ömer–Gecek thermal waters yield reservoir temperatures of 75–155°C. The enthalpy–chloride mixing model, which approximates a reservoir temperature of 125°C for the Ömer–Gecek field, accounts for the diversity in the chemical composition and temperature of the waters by a combination of processes including boiling and conductive cooling of deep thermal water and mixing of the deep thermal water with cold water. It is also determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Ömer–Gecek thermal waters studied by means of the Na–K–Mg triangular diagram, Na–K–Mg–Ca diagram, K–Mg–Ca geoindicator diagram, activity diagrams in the systems composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–CO₂–H₂O phases, log SI diagrams, and finally the alteration mineralogy indicate that most of the spring and low-temperature well waters in the area can be classified as shallow or mixed waters which are likely to be equilibrated with calcite, chalcedony and kaolinite at predicted temperature ranges similar to those calculated from the chemical geothermometers. It was also observed that mineral equilibrium in the Ömer–Gecek waters is largely controlled by CO₂ concentrations.     

Inter-annual and seasonal variations in the air–sea CO2 balance in the central Baltic Sea and the Kattegat

We estimated the net annual air–sea exchange of carbon dioxide (CO₂) using monitoring data from the East Gotland Sea, Bornholm Sea, and Kattegat for the 1993–2009 period. Wind speed and the sea surface partial pressure of CO₂ (pCO₂^w), calculated from pH, total alkalinity, temperature, and salinity, were used for the flux calculations. We demonstrate that regions in the central Baltic Sea and the Kattegat alternate between being sinks (−) and sources (+) of CO₂ within the −4.2 to +5.2 mol m⁻² yr⁻¹ range. On average, for the 1994–2008 period, the East Gotland Sea was a source of CO₂ (1.64 mol m⁻² yr⁻¹), the Bornholm Sea was a source (2.34 mol m⁻² yr⁻¹), and the Kattegat was a sink (−1.16 mol m⁻² yr⁻¹). Large inter-annual and regional variations in the air–sea balance were observed. We used two parameterizations for the gas transfer velocity (k) and the choice varied the air–sea exchange by a factor of two. Inter-annual variations in pCO₂^w between summers were controlled by the maximum concentration of phosphate in winter. Inter-annual variations in the CO₂ flux and gas transfer velocity were larger between winters than between summers. This indicates that the inter-annual variability in the total flux was controlled by winter conditions. The large differences between the central Baltic Sea and Kattegat were considered to depend partly on the differences in the mixed layer depth.     

Photochemistry of Ions at D-region Altitudes of the Ionosphere: A Review

The current state of knowledge of the D-region ion photochemistry is reviewed. Equations determining production rates of electrons and positive ions by photoionization of atmospheric neutral species are presented and briefly discussed. Considerable attention is given to the progress in the chemistry of O⁺(⁴S), O⁺(²D), O⁺(²P), N⁺, N₂ ⁺, O₂ ⁺, NO⁺, N₄ ⁺, O₄ ⁺, NO⁺(N₂), NO⁺(CO₂), NO⁺(CO₂)₂, NO⁺(H₂O) _n for n = 1–3, NO⁺(H₂O)(N₂), NO⁺(H₂O)₂(N₂), NO⁺(H₂O)(CO₂), NO⁺(H₂O)₂(CO₂), O₂ ⁺(H₂O), H₃O⁺(OH), H⁺(H₂O) _n for n = 1–8, O^?, O₂ ^?, O₃ ^?, O₄ ^?, OH^?, CO₃ ^?, CO₄ ^?, NO₂ ^?, NO₃ ^?, ONOO^?, Cl^?, Cl^?(H₂O), Cl^?(CO₂), HCO₃ ^?, CO₃ ^?(H₂O), CO₃ ^?(H₂O)₂, NO₃ ^?(H₂O), NO₃ ^?(H₂O)₂, OH^?(H₂O), and OH^?(H₂O)₂ ions. The analysis of the D-region rocket ion mass spectrometer measurements shows that, among these ions, O₂ ⁺, NO⁺, NO⁺(H₂O), and H⁺(H₂O) _n for n = 1–7 can make the main contribution to the total positive ion number density, and O^?, O₂ ^?, Cl^?, OH^?(H₂O), CO₃ ^?, HCO₃ ^?, NO₃ ^?, ONOO^?, CO₄ ^?, NO₃ ^?(H₂O), NO₃ ^?(H₂O)₂, and ³⁵Cl^?(CO₂) ions can be responsible for the main contribution to the total negative ion number density. Photodetachment of electrons from O^?, Cl^?, O₂ ^?, O₃ ^?, OH^?, NO₂ ^?, and NO₃ ^?, dissociative electron photodetachment of O₄ ^? and OH^?(H₂O), and photodissociation of O₃ ^?, O₄ ^?, CO₃ ^?, CO₄ ^?, ONOO^?, HCO₃ ^?, CO₃ ^?(H₂O), NO₃ ^?(H₂O), O₂ ⁺(H₂O), O₄ ⁺, N₄ ⁺, NO⁺(H₂O), NO⁺(H₂O)₂, H⁺(H₂O) _n for n = 2–4, NO⁺(N₂), and NO⁺(CO₂) are studied, and the photodetachment and photodissociation rate coefficients are calculated using the current state of knowledge on the cross sections of these processes and fluxes of solar radiation.     

Impact of Ca2+ and Mg2+ on the Removal of F− by Magnesium Potassium Phosphate

This study investigates the influence of Ca²⁺ and Mg²⁺ on the removal of F^? by magnesium potassium phosphate (MPP) from water. The kinetic experiments reveal that the F^? concentration decreased from 3.5 to 3.31 mg L^?1 in a single (F^?) system and to 1.45 mg L^?1 in a ternary system (F^?, Ca²⁺, and Mg²⁺) after 1 min, respectively. Thus, the F^? removal efficiencies are found to increase by about 53% with the co‐active effect of Ca²⁺ and Mg²⁺ in the solution. Moreover, Ca²⁺ and Mg²⁺ are almost completely removed in the F^?, Ca²⁺, and Mg²⁺ system. According to the pseudo‐first‐order modeling, the rate constants k for F^?, Ca²⁺, and Mg²⁺ are 0.00348, 0.0106, and 0.0159 min^?1 respectively; thus, Mg²⁺ > Ca²⁺ > F^?. In the ternary system, the removal efficiencies are 53.29–66.03% for F^?, 99.99–100% for Ca²⁺, and 87.21–95.19% for Mg²⁺ with initial pH 5–10. The removal efficiencies of F^? increases with increases in initial concentrations of F^?, Ca²⁺, and Mg²⁺. The removal of F^? is governed by two routes: 1) adsorption by electrostatic interactions and outer sphere surface complexation; 2) co‐precipitation with Ca₃(PO₄)₂, CaHPO₄, Mg₃(PO₄)₂, and Mg(OH)₂.     

Geochemical features of the geothermal CO2-watercarbonate rock system and analysis on its CO2 sources

Taking Huanglong Ravine and Kangding, Sichuan, and Xiage, Zhongdian, Yunnan, as examples, the authors summarize the hydrogeochemical and carbon stable isotopic features of the geothermal CO₂-water-carbonate rock system and analyze the CO₂ sources of the system. It was found that the hydrogeochemical and carbon stable isotopic features of such a system are different from those of shallow CO₂-water-carbonate rock system, which is strongly influenced by biosphere. The former has higher CO₂ partial pressure, and is rich in heavy carbon stable isotope. In addition, such a geothermal system is also different from that developed in igneous rock. The water in the latter system lacks Ca²⁺, and thus, there are few tufa deposits on ground surface, but it is rich in light carbon stable isotope. Further analysis shows that CO₂ of the geothermal CO₂-water-carbonate rock system is a mixture of metamorphic CO₂ and magmatic CO₂.     

Chemical and isotopic signatures of the basement rocks from the Campi Flegrei geothermal field (Naples, southern Italy): inferences about the origin and evolution of its hydrothermal fluids

The Campi Flegrei (Naples, Campanian Plain, southern Italy) geothermal system is hosted by Quaternary volcanic rocks erupted before, during and after the formation of the caldera that represents one of the major structural features in the Neapolitan area. The volcanic products rest on a Mesozoic carbonate basement, cropping out north, east and south of the area. Chemical (major, minor and trace elements) and stable isotope (C, H, O) analyses were conducted on drill-core samples recovered from geothermal wells MF-1, MF-5, SV-1 and SV-3, at depths of ˜ 1100 to 2900 m. The study was complemented by petrographic and SEM examination of thin sections. The water which feeds the system is both marine and meteoric in origin. Mineral zonation typical of a high-temperature geothermal system exists in all the geothermal wells; measured temperatures in wells are as high as ˜ 400 °C. The chemical composition of the waters suggests the existence of two reservoirs: a shallow reservoir (depth < 2000 m) fed by seawater that boiled at 320 °C and became progressively diluted by steam-heated local meteoric water during its ascent; and a deeper reservoir (depth > 2000 m) of hypersaline water. The drill-cores are mainly hydrothermally altered volcanics of trachy-latitic affinity, but some altered pelites and limestones are also present. Published Na, Mg and K concentrations of selected geothermal waters indicate that the hydrothermal fluids are in equilibrium with their host rocks, with respect to K-feldspar, albite, sericite and chlorite. The measured δ¹⁸O_(SMOW) values of rocks range from +4.3 to + 16.5%. The measured δD_(SMOW) values range from − 79 to − 46%. The calculated isotopic composition of the fluids at equilibrium with the samples vary from + 1 to + 8.3%. δ¹⁸O and from − 52 to + 1%. δD. The estimated isotopic composition of the waters at equilibrium with the studied samples confirmed the existence of two distinct fluid types circulating in the geothermal system. The shallower has a marine water signature, while the deeper water has a signature consistent both with magmatic and meteoric origins. In the latter case, the recharge of this aquifer likely occurs at the outcrop of the Mesozoic Limestones surrounding the Campanian Plain; after infiltration, the water percolates through evaporitic layers, becoming hypersaline and D-depleted.     

Effects of an estuarine plume-associated bloom on the carbonate system in the lower reaches of the Pearl River estuary and the coastal zone of the northern South China Sea

We observed a phytoplankton bloom downstream of a large estuarine plume induced by heavy precipitation during a cruise conducted in the Pearl River estuary and the northern South China Sea in May–June 2001. The plume delivered a significant amount of nutrients into the estuary and the adjacent coastal region, and enhanced stratification stimulating a phytoplankton bloom in the region near and offshore of Hong Kong. A several fold increase (0.2–1.8 μg Chl L⁻¹) in biomass (Chl a) was observed during the bloom. During the bloom event, the surface water phytoplankton community structure significantly shifted from a pico-phytoplankton dominated community to one dominated by micro-phytoplankton (>20 μm). In addition to increased Chl a, we observed a significant drawdown of pCO₂, biological uptake of dissolved inorganic carbon (DIC) and an associated enhancement of dissolved oxygen and pH, demonstrating enhanced photosynthesis during the bloom. During the bloom, we estimated a net DIC drawdown of 100–150 μmol kg⁻¹ and a TAlk increase of 0–50 μmol kg⁻¹. The mean sea–air CO₂ flux at the peak of the bloom was estimated to be as high as ∼−18 mmol m⁻² d⁻¹. For an average surface water depth of 5 m, a very high apparent biological CO₂ consumption rate of 70–110 mmol m⁻² d⁻¹ was estimated. This value is 2–6 times higher than the estimated air–sea exchange rate.     

Magmatic degassing at Erta 'Ale volcano,Ethiopia

Here we report measurements of the chemical composition and flux of gas emitted from the central lava lake at Erta 'Ale volcano (Ethiopia) made on 15 October 2005. We determined an average SO₂ flux of ∼ 0.69 ± 0.17 kg s^− 1 using zenith sky ultraviolet spectroscopy of the plume, and molar proportions of magmatic H₂O, CO₂, SO₂, CO, HCl and HF gases to be 93.58, 3.66, 2.47, 0.06, 0.19 and 0.04%, respectively, by open-path Fourier transform infrared (FTIR) spectrometry. Together, these data imply fluxes of 7.3, 0.7, 0.008, 0.03 and 0.004 kg s^− 1 for H₂O, CO₂, CO, HCl and HF, respectively. These are the first FTIR spectroscopic observations at Erta 'Ale, and are also some of the very few gas measurements made at the volcano since the early 1970s (Gerlach, T.M., 1980b. Investigation of volcanic gas analyses and magma outgassing from Erta 'Ale lava lake, Afar, Ethiopia. Journal of Volcanology and Geothermal Research, 7(3–4): 415–441). We identify significant increases in the proportion of H₂O in the plume with respect to both CO₂ and SO₂ across this 30-year interval, which we attribute to the depletion of volatiles in magma that sourced effusive eruptions during the early 1970s and/or to fractional magma degassing between the two active pit craters located in the summit caldera.     

Influence of Atmospheric Solar Radiation Absorption on Photodestruction of Ions at D-Region Altitudes of the Ionosphere

The influence of atmospheric solar radiation absorption on the photodetachment, dissociative photodetachment, and photodissociation rate coefficients (photodestruction rate coefficients) of O^?, Cl^?, O₂ ^?, O₃ ^?, OH^?, NO₂ ^?, NO₃ ^?, O₄ ^?, OH^?(H₂O), CO₃ ^?, CO₄ ^?, ONOO^?, HCO₃ ^?, CO₃ ^?(H₂O), NO₃ ^?(H₂O), O₂ ⁺(H₂O), O₄ ⁺, N₄ ⁺, NO⁺(H₂O), NO⁺(H₂O)₂, H⁺(H₂O) _n for n = 2–4, NO⁺(N₂), and NO⁺(CO₂) at D-region altitudes of the ionosphere is studied. A numerical one-dimensional time-dependent neutral atmospheric composition model has been developed to estimate this influence. The model simulations are carried out for the geomagnetically quiet time period of 15 October 1998 at moderate solar activity over the Boulder ozonesonde. If the solar zenith angle is not more than 90° then the strongest influence of atmospheric solar radiation absorption on photodestruction of ions is found for photodissociation of CO₄ ^? ions when CO₃ ^? ions are formed. It follows from the calculations that decreases in the photodestruction rate coefficients of ions under consideration caused by this influence are less than 2 % at 70 km altitude and above this altitude if the solar zenith angle does not exceed 90°.     

A comparative overview of weathering intensity and HCO3 flux in the world's major rivers with emphasis on the Changjiang,Huanghe, Zhujiang (Pearl) and Mississippi Rivers

In this paper, general relationships of riverine bicarbonate concentrations and fluxes as a function of drainage basin mineral content and runoff are examined using a database of the 25 largest rivers in the world. Specific HCO₃⁻ flux normalized to unit basin area, which peaks in the mid latitudes, was found to be strongly correlated with the carbonate mineral content of river basins, while river HCO₃⁻ concentration was related to the balance of precipitation and evaporation. Within this global context, the weathering patterns of CO₂ in a few large rivers (Changjiang, Huanghe, Pearl, and Mississippi rivers) were examined in further detail. The Zhujiang (Pearl River), especially its largest branch (Xijiang), was characterized by the highest specific weathering rate among all the world's large rivers due to an exceptionally high carbonate mineral content (over 80%) in its drainage basin and its warm and wet environment. It has a moderate level of HCO₃⁻ concentration, however, due to dilution by relatively high precipitation in the watershed. In stark contrast, the Huanghe (Yellow River) has one of the lowest specific weathering rates because of low carbonate mineral content and a dry climate. However, it has a high HCO₃⁻ concentration due largely to the concentrating effects of high evaporative water loss, as a result of arid weather and the agricultural use of water through irrigation systems, as well as carbonate-containing surficial deposits (i.e., loess). The strong correlation between specific HCO₃⁻ fluxes and discharge in all four rivers with different discharge seasonality suggests that higher precipitation in drainage basins promotes higher weathering rates.     

Assessment of groundwater quality and its suitability for drinking and agricultural uses in arid environment

Groundwater quality in Ma’an area was evaluated for its suitability for drinking and agricultural uses by determining the main physical and chemical properties during a 1 year survey study (August 2009 to August 2010). Several samples were collected from ten different wells and analysed for temperature, pH, conductivity, total dissolved solids, total hardness, major cations (Ca²⁺, Mg²⁺, Na⁺ and K⁺), major anions (HCO₃ ^?, Cl^?, NO₃ ^?, SO₄ ^2?, F^? and Br^?) and trace metals (Fe²⁺, Al³⁺, Mn²⁺, Cu²⁺, Zn²⁺, Pb²⁺ and Cd²⁺). The general chemistry of water samples was typically of alkaline earth waters with prevailing bicarbonate chloride. The results showed great variations among the analyzed samples with respect to their physical and chemical parameters. However, most values were below the maximum permissible levels recommended by Jordanian and WHO drinking water standards. The quality assessment shows that in general, the GW in the study area is not entirely fit for direct drinking with respect to EC, and Pb²⁺. According to the residual sodium carbonate and sodium adsorption ratio, the water in the studied wells can be used for irrigational purposes.