Vent fluid chemistry in Bahía Concepción coastal submarine hydrothermal system, Baja California Sur, Mexico

Shallow submarine hydrothermal activity has been observed in the Bahía Concepción bay, located at the Gulf coast of the Baja California Peninsula, along faults probably related to the extensional tectonics of the Gulf of California region. Diffuse and focused venting of hydrothermal water and gas occurs in the intertidal and shallow subtidal areas down to 15 m along a NW–SE-trending onshore–offshore fault. Temperatures in the fluid discharge area vary from 50 °C at the sea bottom up to 87 °C at a depth of 10 cm in the sediments.Chemical analyses revealed that thermal water is enriched in Ca, As, Hg, Mn, Ba, HCO₃, Li, Sr, B, I, Cs, Fe and Si, and it has lower concentrations of Cl, Na, SO₄ and Br than seawater. The chemical characteristics of the water samples indicate the occurrence of mixing between seawater and a thermal end-member. Stable isotopic oxygen and hydrogen composition of thermal samples plot close to the Local Meteoric Water Line on a mixing trend between a thermal end-member and seawater. The composition of the thermal end-member was calculated from the chemistry of the submarine samples data by assuming a negligible amount of Mg for the thermal end-member. The results of the mixing model based on the chemical and isotopic composition indicate a maximum of 40% of the thermal end-member in the submarine vent fluid.Chemical geothermometers (Na/Li, Na–K–Ca and Si) were applied to the thermal end-member concentration and indicate a reservoir temperature of approximately 200 °C. The application of K–Mg and Na/Li geothermometers for vent fluids points to a shallow equilibrium temperature of about 120 °C.Results were integrated in a hydrogeological conceptual model that describes formation of thermal fluids by infiltration and subsequent heating of meteoric water. Vent fluid is generated by further mixing with seawater.     

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.     

Evaluation of reservoir temperatures and local utilization of geothermal waters of the Konkan Coast, India

Geochemical studies on fifteen geothermal manifestations (38–70°C) from the Konkan coast geothermal province of India have been used to evaluate the reservoir temperatures. Activity studies of the minerals and the waters present in the reservoirs suggest that the thermal waters are in equilibrium with montmorillonite, kaolinite and quartz at about 100°C. Reservoir temperatures of these geothermal systems as estimated by geochemical thermometers, are 88 to 128°C, and thus too low for economic electricity production.     

Correlations between microbial indicators, pathogens, and environmental factors in a subtropical Estuary

The objective of this study was to evaluate whether indicator microbes and physical–chemical parameters were correlated with pathogens within a tidally influenced Estuary. Measurements included the analysis of physical–chemical parameters (pH, salinity, temperature, and turbidity), measurements of bacterial indicators (enterococci, fecal coliform, Escherichia coli, and total coliform), viral indicators (somatic and MS2 coliphage), viral pathogens (enterovirus by culture), and protozoan pathogens (Cryptosporidium and Giardia). All pathogen results were negative with the exception of one sample which tested positive for culturable reovirus (8.5 MPN/100 L). Notable physical–chemical parameters for this sample included low salinity (<1 ppt) and high water temperature (31 °C). Indicator bacteria and indicator virus levels for this sample were within average values typically measured within the study site and were low in comparison with levels observed in other freshwater environments. Overall results suggest that high levels of bacterial and viral indicators were associated with low salinity sites.     

Geochemical and hydrogeological characterization of thermal springs in Western Sicily, Italy

Thermal and cold waters from Castellammare–Alcamo (Western Sicily-Italy) were collected between May 1994 and May 1995 and studied for their chemical and isotopic composition. During the same period, mean monthly samples of meteoric water were also collected and measured for their isotopic composition. The main purpose of this study was the characterization of the acquifers and, if possible, of their recharge areas. According to the results obtained, the acquifers were divided into three main groups: (a) selenitic waters, (b) cold carbonatic waters, and (c) deep thermal waters resulting from the mixing of the other two types. Besides a mixing process between carbonatic and selenitic waters, contamination processes of thermal waters by seawater take place during their ascent. The water temperature of the acquifer feeding the thermal springs was estimated by means of various geothermometers to range between 60°C and 97°C. Isotope data on rainwater samples show a wide seasonal variation of both δ and δD values. The fairly constant values of thermal waters through time and the lack of an apparent correlation with the isotopic values of rainwater suggest the existence of a deep circuit determining an almost complete homogenisation of the seasonal variations of the isotopic values.     

Emplacement temperatures of the November 22, 1994 nuée ardente deposits, Merapi Volcano, Java

A study of emplacement temperatures was carried out for the largest of the 22 November 1994 nuée ardente deposits at Merapi Volcano, based mainly on the response of plastic and woody materials subjected to the hot pyroclastic current and the deposits, and to some extent on eyewitness observations. The study emphasizes the Turgo–Kaliurang area in the distal part of the area affected by the nuée ardente, where nearly 100 casualties occurred. The term nuée ardente as used here includes channeled block-and-ash flows, and associated ash-clouds of surge and fallout origins. The emplacement temperature of the 8 m thick channeled block-and-ash deposit was relatively high, 550°C, based mainly on eyewitness reports of visual thermal radiance. Emplacement temperatures for ash-cloud deposits a few cm thick were deduced from polymer objects collected at Turgo and Kaliurang. Most polymers do not display a sharp melting range, but polyethylene terephthalate used in water bottles melts between 245 and 265°C, and parts of the bottles that had been deformed during fabrication molding turn a milky color at 200°C. The experimental evidence suggests that deposits in the Turgo area briefly achieved a maximum temperature near 300°C, whereas those near Kaliurang were <200°C. Maximum ash deposit temperatures occurred in fallout with a local source in the channeled block-and-ash flow of the Boyong river valley; the surge deposit was cooler (180°C) due to entrainment of cool air and soils, and tree singe-zone temperatures were around 100°C.     

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.     

Two-phase separation and fracturing in mid-ocean ridge gabbros at temperatures greater than 700°C

Microthermometric analyses of fluid inclusions on a suite of hydrothermally altered gabbros recovered just south of the eastern intersection of the Kane Fracture Zone and the Mid-Atlantic Ridge, record the highest homogenization temperatures yet reported for mid-ocean ridge hydrothermal systems. Fluid salinities in the high temperature inclusions are more than ten times that of seawater. Multiple generations of fluid inclusions entrapped along healed microfractures exhibit three distinct temperature-compositional groups. We interpret these populations as having been trapped during three separate fracturing events.The earliest episode of brittle failure in the gabbros is represented by coplanar, conjugate vapor-dominated and brine-dominated fluid inclusion arrays in primary apatite. Vapor-dominated inclusions exhibit apparent homogenization temperatures of 400°C and contain equivalent salinities of 1–2 wt.% NaCl. These inclusions are interspersed with liquid-dominated, sulfide-bearing inclusions containing salinities of 50 wt.% NaCl equivalent. These high salinity inclusions remain unhomogenized at temperatures greater than 700°C.Compositional and phase relationships of the fluid inclusions may be accounted for by two-phase separation of a fluid under 1000–1200 bars pressure. These pressures require that fluid entrapment occurred under a significant lithostatic component and indicate a minimum entrapmentdepth of 2 km below the axial valley floor. This depth corresponds to a minimum tectonic uplift of 3 km, in order to emplace the samples at the 3100 m recovery depth. The microfracture networks within magmatic apatites represent fluid flow paths for either highly modified, deeply penetrating seawater or a late stage magmatic aqueous fluid. The inclusions may have formed close to the brittle-ductile transition zone adjacent to an active magma chamber.Following collapse of the high temperature front, lower temperature fluids of definite seawater origin circulated through the open fracture networks, pervasively altering portions of the gabbros. This stage is represented by low-to-moderate (1–7 wt.% NaCl equivalent) salinity inclusions in plagioclase, apatite, epidote, and augite, which homogenize at temperatures of approximately 200–300°C and 400°C. Formation of hydrous mineral assemblages, under greenschist to lower amphibolite facies conditions, resulted in sealing of the vein system and may have resulted in modification of seawater salinities by as much as a factor of two. During or following these later stages of hydrothermal activity the gabbros were emplaced high on the axial walls by differential uplift attending formation of the flanking mountains.     

Sediment and trace element depositional history from the Ajkwa River estuarine mangroves of Irian Jaya (West Papua), Indonesia

Radiotracer ²¹⁰Pb and contaminant copper were used to estimate sediment accumulation rates in 4 cores from the Ajkwa River estuary and mangrove tidal channels in western Irian Jaya. Mass accumulation rates (4.5–13 kg dry wt m⁻² yr⁻¹) were within the envelope of expectations for a region of high rainfall, great river catchment relief, and rapid tectonic uplift of mountains. Copper accumulation rates were enhanced 40 fold in surface sediments, compared to pre-1950 sections of the sediment cores. These recent sediments with enhanced copper concentrations come from Freeport Indonesia mine tailings over the last 27 years. Variations in sediment core profiles of Al, Fe, and organic carbon were small, indicating no great change in bulk sediment composition. Sulfur concentrations decline toward the sediment surface, suggesting a decline in rates of microbial sulfate reduction. Enhanced sediment copper concentrations will be a useful tracer of sediment dispersal from the Ajkwa River estuary along this coast.     

An overview of physical and ecological processes in the Rio de la Plata Estuary

The Rio de la Plata is a large-scale estuary located at 35°S on the Atlantic coast of South America. This system is one of the most important estuarine environments in the continent, being a highly productive area that sustains valuable artisanal and coastal fisheries in Uruguay and Argentina. The main goals of this paper are to summarize recent knowledge on this estuary, integrating physical, chemical and biological studies, and to explore the sources and ecological meaning of estuarine variability associated to the stratification/mixing alternateness in the estuary. We summarized unpublished data and information from several bibliographic sources. From study cases representing different stratification conditions, we draw a holistic view of physical patterns and ecological processes of the stratification/mixing alternateness. This estuary is characterized by strong vertical salinity stratification most of the time (the salt-wedge condition). The head of the estuary is characterized by a well-developed turbidity front. High turbidity constrains their photosynthesis. Immediately offshore the turbidity front, water becomes less turbid and phytoplankton peaks. As a consequence, trophic web in the estuary could be based on two sources of organic matter: phytoplankton and plant detritus. Dense plankton aggregations occur below the halocline and at the tip of the salt wedge. The mysid Neomysis americana, a key prey for juvenile fishes, occurs all along the turbidity front. A similar spatial pattern is shown by one of the most abundant benthic species, the clam Mactra isabelleana. These species could be taken advantage of the particulate organic matter and/or phytoplankton concentrated near the front. Nekton is represented by a rich fish community, with several fishes breeding inside the estuary. The most important species in terms of biomass is Micropogonias furnieri, the main target for the coastal fisheries of Argentina and Uruguay. Two processes have been identified as producing partially stratified conditions: persistent moderate winds (synoptic scale), or low freshwater runoff (interannual scale). Less frequently, total mixing of the salt wedge occurs after several hours of strong winds. The co-dominance of diatoms (which proliferate in highly turbulent environments) and red tides dinoflagellates and other bloom taxa (better adapted to stratified conditions), would indicate great variability in the turbulence strength, probably manifested as pulses. Microplankton and ichthyoplankton assemblages defined for the stratified condition are still recognized during the partially mixed condition, but in this case they occupy the entire water column: vertical structure of the plankton featuring the stratified condition become lost. Bottom fish assemblages, on the contrary, shows persistence under the different stratification conditions, though the dominant species of the groups show some variations. Summarizing, the Río de la Plata Estuary is a highly variable environment, strongly stratified most of the time but that can be mixed in some few hours by strong wind events that occur in an unpredictable manner, generating stratification/partially mixed (less frequently totally mixed) pulses all along the year. At larger temporal scales, the system is under the effects of river discharge variations associated to the ENSO cycle, but their ecological consequences are not fully studied.     

Petrology of Philippine geothermal systems and the application of alteration mineralogy to their assessment

Philippine geothermal systems occur in the vicinity of large Holocene calc-alkaline volcanic complexes. Wells drilled in these areas encountered multiple intrusions; the latest dikes are the subsurface manifestations of the youngest heat source. Commonly, at least two hydrothermal regimes are juxtaposed in a single area, with the latest being in equilibrium with the present temperature and chemical regime.Alteration by neutral-pH water is pervasive and abundant. A contact-metamorphic aureole also occurs near intrusives. Alteration due to acid-sulfate fluids is generally confined to permeable structures. Neutral-pH alteration is divided into four zones on the basis of key clay minerals, and two subzones are defined by calc-silicates. These are the smectite (ambient to 180°C), transition (180–230°C), illite (230–320°C) and biotite (270–340°C) zones. Subzones are defined by epidote (250–340°C) and amphibole (280–340°C). The four main zones of acid alteration are: kaolinite (ambient to 120°C), dickite ± kaolinite (120–200°C), dickite ± pyrophyllite (200–250°C), and pyrophyllite ± illite (230–320°C). Where relict high-temperature alteration reaches the surface, the area being drilled is usually the outflow zone of the present system.These hydrothermal mineral assemblages are used: (1) as geothermometers; (2) to assist in determining the depth at which the production casing will be set during drilling; (3) to estimate fluid pH and other chemical parameters; (4) to predict possible corrosion and scaling tendencies of the fluids; (5) as a measure of permeability and possible cold water influx into wells; (6) as a guide to field hydrology; and (7) to estimate roughly the thickness of the eroded overburden.     

Metal-depleted root zones of the Troodos ore-forming hydrothermal systems, Cyprus

The cupriferous pyrite deposits of Cyprus were precipitated from hydrothermal solutions derived by interaction of contemporaneous seawater with hot mafic rock at the ancient Troodos spreading centre. Here we identify the zones in which this interaction took place. The zones occur in the lower part of the sheeted dyke complex, and within them 30–50% of the rock is made up of epidosite, an epidote-quartz rock, replacing the dykes as sheets and pipes. The epidosites contain abundant fluid inclusions, which give trapping temperatures of 350–400°C or even higher, and contain water normally near seawater in salinity. Zones of epidosite are elongate parallel to the strike of the sheeted dykes, and are up to 1 km wide. The rocks throughout these zones are strongly depleted in Cu and Zn, and the metals removed are sufficient to supply the ore deposits. In fact several large ore deposits lie along strike from zones of epidosite. All of these features support the identification of the epidosites as the hydrothermal reaction zones.The location of the epidosite zones immediately above the gabbros of the plutonic complex supports the hypothesis that the heat to drive the ore-forming systems came from the underlying magma, as is also likely for modern black smoker springs.     

Hydrogeochemical outline of thermal waters and geothermometry applications in Anatolia (Turkey)

The chemical compositions of a total of 120 thermal water samples from four different tectonically distinct regions (Central, North, East and West Anatolia) of Turkey are presented and assessed in terms of geothermal energy potential of each region through the use of chemical geothermometers. Na–Ca–HCO₃ type waters are the dominant water types in all the regions except that Na–Cl type waters are typical for the coastal areas of West Anatolia and for a few inland areas of West and Central Anatolia where deep water circulation exists. The discharge temperature of the springs ranges up to 100°C, and the bottom-hole temperatures in drilled wells up to 232°C. Geothermometry applications yield reservoir temperatures of about 125°C for Central Anatolia, 110°C for North Anatolia, 136°C for East Anatolia and 251°C for West Anatolia, the latter agreeing with some of the bottom hole temperatures measured in drilled wells. The results reveal that the highest geothermal energy potential in Turkey is associated with the West Anatolian extensional tectonics which provides a regional, deep-seated heat source and a widespread graben system allowing deep circulation of waters. The North Anatolian region, bounded to the south by the dextral North Anatolian Fault along which most of the geothermal sites are located, has the lowest energy potential, probably due to the restriction of the heat source to local magmatic activities confined to pull-apart basins. The East Anatolian region (undergoing contemporary compression) and the Central Anatolian region (where the compressional regime in the east is converted to the extensional regime in the west) have moderate energy potential. Although the recently active volcanoes suggest the presence, at depth, of still cooling magma chambers that are potential heat sources, the lack of well-developed fault systems is probably responsible for the comparatively low energy potential of these regions. Almost all the thermal waters of Turkey are saturated with respect to calcite and, hence, have a significant calcite scaling potential which is particularly high for West Anatolian waters.     

A reconnaissance geochemical study of La Primavera geothermal area, Jalisco, Mexico

The Sierra La Primavera, a late Pleistocene rhyolitic caldera complex in Jalisco, México, contains fumaroles and large-discharge 65°C hot springs that are associated with faults related to caldera collapse and to later magma insurgence. The nearly-neutral, sodium bicarbonate, hot springs occur at low elevations at the margins of the complex, whereas the water-rich fumaroles are high and central.The Comisión Federal de Electricidad de México (CFE) has recently drilled two deep holes at the center of the Sierra (PR-1 and Pr-2) and one deep hole at the western margin. Temperatures as high as 285°C were encountered at 1160 m in PR-1, which produced fluids with 820 to 865 mg/kg chloride after flashing to one atmosphere. Nearby, PR-2 encountered temperatures to 307°C at 2000 m and yielded fluids with chloride contents fluctuating between 1100 and 1560 mg/kg after flashing. Neither of the high-temperature wells produced steam in commercial quantities. The well at the western margin of the Sierra produced fluids similar to those from the hot springs. The temperature reached a maximum of 100°C near the surface and decreased to 80°C at 2000 m.Various geothermometers (quartz conductive, Na/K, Na-K-Ca, δ¹⁸O(SO₄-H₂O) and D/H (steam-water) all yield temperatures of 170 ± 20°C when applied to the hot spring waters, suggesting that these spring waters flow from a large shallow reservoir at this temperature. Because the hot springs are much less saline than the fluids recovered in PR-1 and PR-2, the mixed fluid in the shallow reservoir can contain no more than 10–20% deep fluid. This requires that most of the heat is transferred by steam. There is probably a thin vapor-dominated zone in the central part of the Sierra, through which steam and gases are transferred to the overlying shallow reservoir. Fluids from this reservoir cool from 170°C to 65°C by conduction during the 5–7 km of lateral flow to the hot springs.     

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.     

Seasonal variations in pCO2 and its controlling factors in surface seawater of the northern East China Sea

Surface partial pressure of CO₂ (pCO₂), temperature, salinity, nutrients, and chlorophyll a were measured in the East China Sea (ECS; 31°30′–34°00′N to 124°00′–127°30′E) in August 2003 (summer), May 2004 (spring), October 2004 (early fall), and November 2005 (fall). The warm and saline Tsushima Warm Current was observed in the eastern part of the survey area during four cruises, and relatively low salinity waters due to outflow from the Changjiang (Yangtze River) were observed over the western part of the survey area. Surface pCO₂ ranged from 236 to 445 μatm in spring and summer, and from 326 to 517 μatm in fall. Large pCO₂ (values >400 μatm) occurred in the western part of the study area in spring and fall, and in the eastern part in summer. A positive linear correlation existed between surface pCO₂ and temperature in the eastern part of the study area, where the Tsushima Warm Current dominates; this correlation suggests that temperature is the major factor controlling surface pCO₂ distribution in that area. In the western part of the study area, however, the main controlling factor is different and seasonally complex. There is large transport in this region of Changjiang Diluted Water in summer, causing low salinity and low pCO₂ values. The relationship between surface pCO₂ and water stability suggests that the amount of mixing and/or upwelling of CO₂-rich water might be the important process controlling surface pCO₂ levels during spring and fall in this shallow region. Sea–air CO₂ flux, based on the application of a Wanninkhof [1992. Relationship between wind speed and gas exchange over the ocean. Journal of Geophysical Research 97, 7373–7382] formula for gas transfer velocity and a set of monthly averaged satellite wind data, were −5.04±1.59, −2.52±1.81, 1.71±2.87, and 0.39±0.18 mmol m⁻² d⁻¹ in spring, summer, early fall, and fall, respectively, in the northern ECS. The ocean in this study area is therefore a carbon sink in spring and summer, but a weak source or in equilibrium with the atmosphere in fall. If the winter flux value is assumed to have been the mean of autumnal and vernal values, then the northern ECS absorbs about 0.013 Pg C annually. That result suggests that the northern ECS is a net sink for atmospheric CO₂, a result consistent with previous studies.     

Geothermal assessment of the island of ischia (southern Italy) from isotopic and chemical composition of the delivered fluids

The Ischia geothermal system is hosted by silicic rocks of the Quaternary Potassic Roman Province, in southern Italy. Exploration drilling down to 1156 m depth in the mid-1950s provided information on boiling profiles (up to 250°C) and on the depth and permeability of the potential reservoirs. Discharge fluid samples were collected and analyzed to define the inflow of surrounding seawater (C1 ranges from 2.5 to 20 g/kg) into the system.Analyses of samples from surface manifestations and shallow wells collected during 1983 and 1988 point to the existence of three distinct mixing regimes, involving three water components. A dishomogeneous body of diluted water (Cl less than 2.5 g/kg), that occurs at depths > 700 m and reequilibrates at 240°C at least, is overlain by an aquifer of groundwater variably mixed with variably seawater (Cl from 4 to 10 g/kg), which tends to reequilibrate at 160°C. Steam-heated waters locally develop and act as dilutants of the rising geothermal fluids.Dilution, mixing, and evaporation of the ascending chloride fluids are supported by oxygen and hydrogen isotopic data the thermal waters being enriched in ¹⁸O and D with respect to local meteoric water by up to 7 and 30‰, respectively. The relative composition of the major cations in thermal solutions was used to discriminate the two main groups of thermal waters, the reservoir temperatures of which are estimated from the Na/K-gethermometer. K-Mg geothermometer indicates reequilibration in near-surface conditions.The isotopic composition of the fumarolic steam varies from −7 to −12‰ in ∂⁸O and from − 35 to − 70‰ in ∂D, in agreement with a deep mixed fluid that boils adiabatically from 240 to 80°C. The deuterium content of the H₂O-H₂ pair gives enrichment factor of about 830‰, corresponding to equilibrium temperature conditions slightly higher than the surface boiling temperatures. The ∂¹³C of CO₂is almost constant at −4.5‰ (1δ=0.4), suggesting an important magmatic contribution, and the ∂¹⁸O values of CO₂appears to in equilibrium with accompanying steam at the measured temperatures.The CO₂/Ar and H₂/Ar chemical ratios have been used to derive aquifer temperatures, the values obtained being consistent with those of solute geothermometers.     

Multi-stage fluid circulation in a hydraulic fracture breccia of the Larderello geothermal field (Italy)

The deep well MV5A, drilled in the western part of the Larderello geothermal field, crossed a 20-cm-thick hydraulic fracture breccia unit at a depth of 1090 m below ground level (b.g.l.). This breccia occurs in a fine-grained Triassic metasandstone and consists of angular to subangular clasts of up to some centimeters in size. Pervasive alteration has affected the breccia clasts and wall rock around the breccia, with the formation of Mg–Fe chlorite. After such alteration, hydrothermal circulation caused the precipitation of two generations of calcite cement. Then, ankerite partially replaced these two calcite generations. Ankerite also precipitated in late veinlets with chlorite. Late hydrothermal activity led to the crystallization of albite, quartz and finally, anhydrite. The calcite contains vapor-rich inclusions and two populations of liquid-rich (L1 and L2) inclusions. L1 inclusions are characterized by homogenization temperatures between 304 and 361°C and salinities from 7.4 to 11.6 wt.% NaCl equivalent; L2 inclusions revealed homogenization temperatures in the range of 189–245°C and salinities from 2.6 to 6.3 wt.% NaCl equivalent. The fluids contained in L2 inclusions were probably trapped coevally with some vapor-rich inclusions under boiling conditions after the L1 inclusions formed. Some of the abundant vapor-rich inclusions in calcite may also represent early, low-temperature inclusions affected by decrepitation and/or stretching and/or leaking during L1 trapping. The liquid-rich (L) inclusions trapped at later stages in ankerite, albite and anhydrite display, respectively, homogenization temperature ranges of 189–198°C, 132–145°C, and 139–171°C, and salinities ranging from 1.6 to 1.7 wt.% NaCl equivalent, 1.4 to 2.1 wt.% NaCl equivalent and 3.7 to 6.2 wt.% NaCl equivalent. The inclusions studied record the evolution, over time, of the fluids flowing in the breccia level: L1 inclusions capture high-temperature fluid (about 300 to 350°C) of high salinity (around 10 wt.% NaCl equivalent) at above-hydrostatic pressures (up to about 150 bar). The L2 inclusions in calcite and liquid-rich inclusions in ankerite and albite represent subsequent hydrothermal fluid evolution toward lower temperatures (about 250 to 130°C), pressures (45 to a few bar) and salinities (6.3 to 1.4 wt.% NaCl equivalent). During this stage, boiling processes and infiltration of meteoric waters probably occurred. Finally, moderately saline fluids (around 5 wt.% NaCl equivalent) at a temperature (about 160°C) close to that of present-day in-hole measurements was trapped in the anhydrite inclusions. The liquids trapped in liquid-rich inclusions circulated at 41,000 years (maximum age of calcite) or later. This age represents an upper limit for the development of vapor-dominated condition, in this part of the geothermal system. The fluids circulating at the breccia level were probably meteoric and/or connate waters. These fluids may have interacted with the anhydrite and carbonate bearing formations present in the Larderello area. The occurrence of the hot and saline fluids, trapped in L1 inclusions at above-hydrostatic pressure, suggests that similar fluids but with higher pressure (≥167 bar) and temperature (≥360°C) may have been responsible for rock fracturing.     

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.     

Seasonal variation of water column structure and sediment transport in a mud depo-center off the Zhejiang-Fujian coast in China

Two surveys were conducted in December, 2008, and August, 2009, in the mud depo-center off the Zhejiang-Fujian coast (MDZFC) in the inner shelf of East China Sea to depict the seasonal variation of the water column structure and analyze the factors responsible for the variation. The results were also used to discuss the sediment transport process and formation mechanism of the MDZFC. The water column structures varied significantly between the two surveys, with respect to the temperature, salinity, and turbidity. The summer water body, with relatively high temperatures and salinities, was evidently stratified with respect to the temperature, whereas the salinity remained constant throughout the water column. The stratification restricts sediment resuspension and transport. From the north to the south, the temperature in the middle-bottom water layer slightly increased, whereas the salinity remained mostly constant. In winter, the water body, with relatively low temperatures and salinities, was well mixed vertically. The temperature and salinity both increased from the surface to the bottom toward the east (deep water) and the south. A wedge-shaped water mass, which appears as a coastal upwelling, with relatively low temperature and high salinity in summer and relatively high temperature and high salinity in winter, spread landward along the sea floor, from the sea deeper than 50 m, whereas the extension was relatively stronger in winter. The water turbidity in winter was clearly higher than in summer. In the surface layer, the turbidity was generally greater than 5 FTU in winter and less than 1 FTU in summer. In the bottom layer, the turbidity was much greater than 200 FTU in winter and slightly greater than 50 FTU in summer. Moreover, the turbid water layer close to the sea floor in winter can reach into an area deeper than 50 m with a thickness of over 10 m; however, it was only limited to only 30-m-deep water with a thickness of 5 m in summer. The differences of marine sedimentary environment in the MDZFC were attributed to the seasonal variations of hydrodynamics environment, weather conditions, sediment supplies, and seasonal circulations. The results suggest that winter is the key season for particle transportation and deposition. The bottom turbid layer is the primarily channel of sediment transport, and the upwelling currents and the oceanic front systems play an important role in the sediment deposit processes and the formation of the MDZFC.