Sources of chloride in hydrothermal fluids from the Valles caldera, New Mexico: a Cl study

The Valles caldera in New Mexico hosts a high-temperature geothermal system, which is manifested in a number of hot springs discharging in and around the caldera. In order to determine the fluid pathways and the origin of chloride in this system, we measured ³⁶Cl/Cl ratios in waters from high-temperature drill holes and from surface springs in this region. The waters fall into two general categories: recent meteoric water samples with low Cl⁻ concentrations (< 10 mg/L) and relatively high ³⁶Cl/Cl ratios [(300–1000) × 10⁻¹⁵]; and geothermal brines with high Cl⁻ concentrations (800–9400 mg/L) but low ³⁶Cl/Cl ratios [(11–26) × 10⁻¹⁵]. The ³⁶Cl/Cl ratios for meteoric waters are slightly higher than expected for this region, suggesting a small addition of anthropogenic ³⁶Cl. Because of low ³⁶Cl/Cl ratios and high Cl⁻ concentrations in the brines, chloride in these waters must be derived from subsurface sources. A comparison between the observed ³⁶Cl/Cl ratios in the brines and those calculated for potential source formations in this region indicates that the present host formations, mainly volcanic tuffs, cannot be major sources of chloride, and that formations at greater depth, such as the Paleozoic and Precambrian formations are more likely to be sources of chloride in the brines. The results suggest that brines are meteoric waters which penetrated into the basement where they derive chloride from leaching of basement rocks and/or from saline pore fluids trapped there, along with likely addition of chloride from Paleozoic strata. Although these fluids have since come to reside in the intracaldera volcanic sequence after convective upwelling, they do not derive much Cl⁻ from the volcanic strata; and residence times of fluids in the volcanics are < 100,000 years.     

S, O and Sr isotope systematics of active vent materials from the Mariana backarc basin spreading axis at 18°N

Stable isotope ratios of S, O and Sr have been measured for active vent materials which were first found and sampled in April 1987 from the Mariana backarc spreading axis at 18°N. Chimneys consisted mostly of barite with a lesser proportion of sulfide minerals such as sphalerite, galena, chalcopyrite and pyrite. Theδ³⁴S values of sphalerite and galena taken from several chimneys and various parts of a chimney showed a narrow range from 2.1 to 3.1‰, suggesting uniform conditions of fluid chemistry during chimney growth. The sulfur isotopic results imply a contribution of hydrogen sulfide reduced from seawater sulfate in the deep hydrothermal reaction zone, considering that fresh glasses of the Mariana Trough basalts haveδ³⁴S= −0.6 ± 0.3‰. Sulfur isotopic compositions of hydrogen sulfide in the high temperature vent fluids (δ³⁴S= 3.6–4.8‰) which are higher than those of the sulfide minerals suggest the secondary addition of hydrogen sulfide partially reduced from entrained seawater SO₄²⁻ at a basal part of the chimneys. This interpretation is consistent with theδ³⁴S values of barite (21–22‰) that are higher than those of seawater sulfate. The residence time of the entrained SO₄²⁻ was an order of an hour on a basis of oxygen isotopic disequilibrium of barite. Strontium isotopic variations of barite and vent waters indicated that Sr in barite was mostly derived from the Mariana Trough basalts with a slight contribution from Sr in circulating sea-water, and that 10–20% mixing of seawater with ascending hydrothermal fluids induced precipitation of barite at the sea-floor.     

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

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

In-situ neutron flux,Cl production and groundwater evolution in crystalline rocks at Stripa, Sweden

The meteoric input of³⁶Cl due to cosmogenic or nuclear-weapon-produced³⁶Cl cannot contribute significantly to the³⁶Cl present in the saline groundwaters (up to 700 mg l⁻¹ Cl⁻) from the Stripa granite. The extent of in-situ production of³⁶Cl has been estimated on the basis of the neutron fluxes within the granite and its surrounding leptite. The³⁶Cl present in the groundwaters is attributed to either admixture of labelled Cl⁻ from the leptite with Cl⁻ from the granite or to the total derivation of groundwater chlorinity within the leptite followed by radiochemical ingrowth of³⁶Cl during subsequent groundwater residence within the granite. The chloride derived from the leptite may be either matrix chloride or chloride from an external source which has had a long residence time within the leptite. The implications of³⁶Cl in-situ production for the estimation of groundwater residence times and for the geochemical evolution of groundwater chlorinity are discussed.     

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

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

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.     

Organic biomarkers for tracing carbon cycling in the Gulf of Papua (Papua New Guinea)

Sediment traps were deployed in the Gulf of Papua in June–July 1997, to determine fluxes of organic matter and inorganic elements from the photic zone to deeper waters at the base of the continental slope and in the northern Coral Sea. Three stations, ranging from 900 to 1500 m depth, had “shallow” traps at 300 m below the water surface and “deep” traps set 100 m above the bottom. Infiltrex II water samplers collected particulate and dissolved organic matter from the Fly, Purari and Kikori rivers, and near-surface water from the shelf of the Gulf of Papua. Samples were analysed for molecular organic biomarkers to estimate the sources of organic carbon and its cycling processes.Dry weight fluxes from the shallow traps ranged from 115 to 181 mg m⁻² day⁻¹ and particulate organic carbon (POC) fluxes ranged from 1.2 to 1.9 mM OC m⁻² d⁻¹ with molar organic carbon to particulate nitrogen ratios (C/N) ranging from 6.0 to 6.5. Fluxes in deep traps were likely influenced by both early diagenesis and entrapment of resuspended shelf sediments. Dry weight fluxes in deep traps ranged from 106 to 574 mg m⁻² day⁻¹ and POC fluxes ranged from 0.6 to 1.5 mM OC m⁻² d⁻¹, with C/N ratios ranging from 8.5 to 10.8. ¹³C/¹²C ratios were −20.2‰ to −21.7‰ in all trap samples, indicating that most of the settling POC was “marine-derived”. Shallow traps had δ¹⁵N values of 6.3‰ to 7.2‰ while the values in deep traps were 4.9–5.0‰, indicating the N-rich near-surface OC was less degraded than that in the deep traps. The biogenic lipids consisted of hydrocarbon, sterol and fatty acid biomarkers indicative of marine zooplankton, phytoplankton and bacteria. Sterol markers for diatoms and dinoflagellates were abundant in the water samples. Highly branched isoprenoid alkenes, usually attributable to diatoms, were also detected in both water and shallow traps. Traces of C₂₆–C₃₄ n-alcohols indicative of land–plant biomarkers, were found in river water samples and in the shallow sediment traps. A large unresolved complex mixture (UCM) of hydrocarbons, and a uniform distribution of n-alkanes, indicative of petroleum hydrocarbons, were also detected in the traps. Hopane and sterane biomarkers detected in the trap oil were characteristic of a marine carbonate source, and the aromatic hydrocarbon composition distinguished at least two different oil signatures.We concluded that mass and POC fluxes were similar to those reported for other continental shelves and marginal oceans in tropical and subtropical regions. There was a dramatic decrease in POC as particles sank, due to zooplankton repackaging and photochemical and bacterial decomposition. Carbon isotopic and biomarker patterns showed most of the POC in the sediment traps was marine-sourced with only traces of terrestrial input. There was a significant flux of petroleum, which may signal the existence of natural petroleum seeps in this region.     

Chemical variations of tephra-fall deposit leachates for three eruptions from Popocatépetl volcano

Leachates from ash samples of the Popocatépetl eruptions of April 30, 1996, May 12, 1997, and October 17, 1998 settled at different distances from the crater were analyzed for anions (SO₄²⁻, Cl⁻, F⁻) and some metals. This study is aimed at determining the causes of the compositional variations of the leachates, to assist the assessment of water, soil and crop contamination due to ash deposits. Different behavior was observed in the ion concentrations with distance for the three eruptions. On April 30, 1996, SO₄²⁻ and F⁻ concentrations increased with distance, and Cl⁻ remained almost constant. On May 12, 1997, concentrations of the three anions decreased with distance. On October 17, 1998, F⁻, Cl⁻ and SO₄²⁻ increased more than three-fold with distance. Tephra size distributions were also different for the three eruptions. The observed trends of the leachates’ anion concentrations may have different causes: the type and intensity of the eruptions, the distribution of the tephra sizes, the degree of interaction of the tephras with volcanic gases, humidity, static charge, the original characteristics of the solid material, the transport time from the crater to the site of settling, and the relative angle between the wind direction and the sampling line. Enrichment factors and concentration trends for metals with distance suggest that Co, Ni, Cu and Pb in the leachates resulted mostly from volcanic gas adsorption.     

Coupling of early diagenetic processes and sedimentary dynamics in tropical shelf environments: the Gulf of Papua deltaic complex

Tropical mobile mud belts represent a major class of biogeochemical and diagenetic systems characterized by extensive and frequent physical reworking of fine-grained, organic-rich deposits underlying oxygenated waters. Large regions of the Gulf of Papua, Papua New Guinea deltaic complex are dominated by such conditions. A reworked mud belt lies within the inner shelf between 10 and 20 m depth on a sedimentary clinoform derived from coalescing deltas. Deposits across the topset are typically suboxic, nonsulfidic over the upper 0.5–1 m, and have low to moderate maximum pore water concentrations of dissolved Fe(II) and Mn(II) (100–200, but up to 800 μM). Sediments are reactive, with surficial ΣCO₂ production 0.1–0.3 mM d⁻¹ and benthic O₂ fluxes 23±15 mmol m⁻² d⁻¹ (upper 20 cm). The highest rates occur within inner topset deposits (10–20 m) and near the high accumulation rollover region of the topset–foreset beds (40–50 m). Lower rates are found inshore along intertidal channels—mangrove fringe and within scoured or exposed consolidated deposits of the middle topset region. Remineralization rate patterns are independent of relative dominance by terrestrial or marine carbon in sediments. Dissolved O₂ usually penetrates 2–5 mm into surface sediments when macrofaunal burrows are absent. More than 75% of the highly reactive sedimentary Fe(III) pool (350–400 μmol g⁻¹) is typically diagenetically reduced in the upper 0.5 m. Pore water can be measureably depleted at depths >0.5 m, but dissolved H₂S generally remains below detection over the upper 1–2 m. As in other deltaic topset regions, concentration gradients often indicate that compared to many marine deposits of similar sediment accumulation rates, relatively refractory C_org is supplied to the SO₄ reducing zone. Sedimentary C/S ratios are 4–6 within the suboxic topset regions but decrease to <3 in offshore foreset beds where sulfidic diagenesis dominates. Only 15–20% of the diagenetically reduced Fe(II) is pyritic and a maximum of 10–25% is carbonate, implying that most Fe(II) is associated with authigenic or lithogenic silicates or oxides. The dominance of suboxic, nonsulfidic diagenetic processes reflect coupling between delivery of oxide-rich terrestrial debris, remobilization and reoxidation of deposits, and repetitive entrainment/remineralization of both labile and refractory organics. Distinct sedimentary indicators of reactive, suboxic mobile mud belts within tropical climatic zones are: abundant total highly reactive Fe (ΣFeR )>300 μmol g⁻¹; most reactive Fe is diagenetically reduced (ΣFe(II)/ΣFeR0.7–0.8); the proportion of diagenetically reduced Fe present as pyrite is low (Py–Fe(II)<0.2); C/S 4–8; and C_org/particle surface area <0.4 (mg C m⁻²). These depositional environments must be most common in tropical climates during high sea stand.     

Chloride source delineation in an urban-agricultural watershed: Deicing agents versus agricultural contributions

Analyses (n = 525) of chloride (Cl⁻), bromide (Br⁻), nitrate as nitrogen (NO₃-N), sodium (Na⁺), calcium (Ca²⁺) and potassium (K⁺) in stream water, tile-drain water and groundwater were conducted in an urban-agricultural watershed (10% urban/impervious, 87% agriculture) to explore potential differences in the signature of Cl⁻ originating from an urban source as compared with an agricultural source. Only during winter recharge events did measured Cl⁻ concentrations exceed the 230 mg/L chronic threshold. At base flow, nearly all surface water and tile water samples had Cl⁻ concentrations above the calculated background threshold of 18 mg/L. Mann–Whitney U tests revealed ratios of Cl⁻ to Br⁻ (p = .045), to NO₃-N (p < .0001), to Ca²⁺ (p < .0001), and to Na⁺ (p < .0001) to be significantly different between urban and agricultural waters. While Cl⁻ ratios indicate that road salt was the dominant source of Cl⁻ in the watershed, potassium chloride fertilizer contributed as an important secondary source. Deicing in watersheds where urban land use is minimal had a profound impact on Cl⁻ dynamics; however, agricultural practices contributed Cl⁻ year-round, elevating stream base flow Cl⁻ concentrations above the background level.     

Geochemical comparison between minettes and kersantites from the Western European Hercynian orogen: trace element and PbSrNd isotope constraints on their origin

Trace element and isotopic characteristics of late Carboniferous to early Permian minettes and kersantites have been determined. These lamprophyres have been sampled throughout the Western European Hercynian orogen, from Brittany to the west to Schwarzwald to the east. In spite of sharp petrological differences reflected by mineralogy and major element geochemistry, minettes and kersantites exhibit close identity with respect to trace element and isotopic features. These features comprise enrichment in incompatible elements, highCs/Rb and lowCe/Pb ratios, Ta and Ti relative depletion, high abundance in transition elements and highNi/Mg ratios. Pb isotope ratios are undistinguishable from those measured on Hercynian continental crust. Initial¹⁴³Nd/¹⁴⁴Nd ratios are between0.5120 (ε_i −5) and0.5122 (ε_i −1) for minettes and kersantites whereas initial⁸⁷Sr/⁸⁶Sr ratios vary between 0.7055–0.710 for minettes and 0.707–0.708 for kersantites. No simple mixing relations are visible on RbSr and SmNd isochron diagrams. The exceptional homogeneity of these geochemical characteristics along a 1000 km traverse does not allow for an hypothesis of enrichment through upper level assimilation and thus leads to propose that these rocks originated through melting of a mantle enriched by recycling of crustal material.     

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.     

Chemical and stable isotopic models for boundary creek warm springs, southwestern Yellowstone National Park, Wyoming

Thermal springs of the Boundary Creek hydrothermal system in the southwestern part of Yellowstone Park outside the caldera boundary vary in chemical and isotopic composition, and temperature. The diversity may be accounted for by a combination of processes including boiling of a deep thermal water, mixing of the deep thermal water with cool meteoric water and/or with condensed steam or steam-heated meteoric water, and chemical reactions with surrounding rocks. Dissolved-silica, Na⁺, K⁺ and Ca²⁺ contents of the thermal springs could result from a thermal fluid with a temperature of 200 ± 20°C. Chloride-enthalpy and silica-enthalpy mixing models suggest mixing of 230°C, 220 mg/l Cl⁻ thermal water with cool, low-Cl⁻ components. A 350 to 390°C component with Cl⁻ ≥ 300 mg/l is possibly present in thermal springs inside the caldera but is not required to fit observed spring chemical and isotopic compositions. Irreversible mass transfer models in which a low-temperature water reacts with volcanic glass as it percolates downward and warms, can account for observed pH and dissolved-silica, K⁺, Na⁺, Ca²⁺ and Mg²⁺ concentrations, but produces insufficient Cl⁻ or F⁻ for measured concentrations in the warm springs. The ratio of a_Na/a_H, and Cl⁻ are best accounted for in mixing models. The water-rock interaction model fits compositions of acid-sulfate waters observed at Summit Lake and of low-Cl⁻ waters involved in mixing.The cold waters collected from southwestern Yellowstone Park have δD values ranging from −118 to −145 per mil and δ¹⁸O values of −15.9 to −19.4 per mil. Two samples from nearby Island Park have δD values of −112 and −114 per mil and δ¹⁸O values of −15.1 and −15.3 per mil. All samples of thermal water plot significantly to the right of the meteoric water line. The low Cl⁻ and variable δD values of the thermal waters indicate isotopic compositions are derived by extensive dilution with cold meteoric water and by steam separation on ascent to the surface. Many of the hot springs with higher δD values may contain in addition a significant amount of high-D, low-Cl⁻, acid-sulfate or steam-heated meteoric water. Mixing models, Cl⁻ content and isotopic compositions of thermal springs suggest that 30% or less of a deep thermal component is present. For example, the highest-temperature springs from Three Rivers, Silver Scarf and Upper Boundary Creek thermal areas contain up to 70% cool meteoric water and 30% hot water components, springs at Summit Lake and Middle Boundary Creek spring 57 are acid-sulfate or steam-heated meteoric water; springs 27 and 48 from Middle Boundary Creek and 49 from Mountain Ash contain in excess of 50% acid-sulfate water; and Three Rivers spring 46 and Phillips could result from mixing hot water with 55% cool meteoric water followed by mixing of acid-sulfate water. Extensive dilution by cool meteoric water increases the uncertainties in quantity and nature of the deep meteoric, thermal component.     

Groundwater mineralisation processes in Mediterranean semi‐arid systems (Cap‐Bon,North east of Tunisia): hydrogeological and geochemical approaches

The groundwater of the Korba plain represents major water resources in Tunisia. The Plio‐Quaternary unconfined aquifer of the Cap‐Bon (north‐east Tunisia) is subject to the intensive agricultural activities and high groundwater pumping rates due to the increasing of the groundwater extraction. The degradation of the groundwater quality is characterized by the salinization phenomena. Groundwater were sampled and analysed for physic‐chemical parameters: Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^‐, SO₄^2‐, HCO₃^‐, NO₃^‐, pH, electrical conductivity (EC), and the temperature (T°). The hydrochemical analysis is coupled with the calculation of the saturation indexes (SI gypsum, SI halite, SI calcite and SI dolomite), ionic derivation and with the ion correlations compared to chloride concentrations: Na⁺/ Cl^‐, Ca²⁺/ Cl^‐ and Mg²⁺/ Cl^‐ ratios. Seawater fractions in the groundwater were calculated using the chloride concentration. Those processes can be used as indicators of seawater intrusion progression. EC methods were also conducted to obtain new informations on the spatial scales and dynamics of the fresh water–seawater interface of coastal groundwater exchange. The mixing zone between freshwater and saltwater was clearly observed from the EC profile in the investigated area where a strong increase in EC with depth was observed, corresponding to the freshwater and saltwater interface. Results of hydrochemical study revealed the presence of direct cation exchange linked to seawater intrusion and dissolution processes associated with cations exchange. These results, together with EC investigation, indicated that the groundwater is affected by seawater intrusion and is still major actor as a source of salinization of the groundwater in Korba coastal plain. Further isotopic and hydrological investigations will be necessary to identify and more understood the underlying mechanisms. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

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

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

Deposition, mineralization, and storage of carbon and nitrogen in sediments of the far northern and northern Great Barrier Reef shelf

The flow of carbon and nitrogen in sediments of the far northern and northern sections of the Great Barrier Reef continental shelf was examined. Most of the organic carbon (81–94%) and total nitrogen (74–92%) depositing to the seabed was mineralized, with burial of carbon (6–19%) and nitrogen (8–20%) being proportionally less on this tropical shelf compared with other non-deltaic shelves. Differences in carbon and nitrogen mineralization among stations related best to water depth and proximity to river basins, with rates of mineralization based on net ∑CO₂ production ranging from 17 to 39 ( mean=23) mmol C m⁻² d⁻¹. The overall ratio of O₂:CO₂ flux was 1.3, close to the Redfield ratio, implying that most organic matter mineralized was algal. Sulfate reduction was estimated to account for ≈30% (range: 6–62%), and denitrification for ≈5% (range: 2–13%), of total C mineralization; there was no measurable CH₄ production. Discrepancies between ∑CO₂ production across the sediment–water interface and sediment incubations suggest that as much as 5 mmol m⁻² d⁻¹ (≈25% of ∑CO₂ flux) was involved in carbonate mineral formation. Most microbial activity was in the upper 20 cm of sediment. Rates of net NH₄⁺ production ranged from 1.6 to 2.7 mmol N m⁻² d⁻¹, with highly variable N₂ fixation rates contributing little to total N input. Ammonification and nitrification rates were sufficient to support rapid rates of denitrification (range: 0.1–12.4 mmol N m⁻² d⁻¹). On average, nearly 50% of total N input to the shelf sediment was denitrified. The average rates of sedimentation, mineralization, and burial of C and N were greater in the northern section of the shelf than in the far northern section, presumably due to higher rainfall and river discharge, as plankton production was similar between regions. The relative proportion of plankton primary production remineralized at the seafloor was in the range of 30–50% which is at the high end of the range found on other shelves. The highly reactive nature of these sediments is attributed to the deposition of high-quality organic material as well as to the shallowness of the shelf, warm temperatures year-round, and a variety of physical disturbances (cyclones, trawling) fostering physicochemical conditions favorable for maintaining rapid rates of microbial metabolism. The rapid and highly efficient recycling of nutrients on the inner and middle shelf may help to explain why the coral reefs on the outer shelf have remained unscathed from increased sediment delivery since European settlement.     

Geochemical characteristics of Yamadağı volcanics in central east Anatolia: an example from collision-zone volcanism

Neogene Yamadağı volcanic rocks consist of basaltic trachyandesite, trachyandesite, andesite, and dacite. The major- and trace-element chemistry indicates that the lavas are dominantly calc-alkaline and mildly alkaline in character, sodic in nature, and intermediate to acidic in composition. REE and trace-element patterns of volcanic rocks are similar to those typical of within plate magmatics. Volcanic rocks have low ⁸⁷Sr/⁸⁶Sr (0.70389–0.70633) and high ¹⁴³Nd/¹⁴⁴Nd ratios (0.51267–0.51276) and mostly plot within the mantle array of the isotope ratio diagram. The linear correlations among ⁸⁷Sr/⁸⁶Sr−¹⁴³Nd/¹⁴⁴Nd, SiO₂−⁸⁷Sr/⁸⁶Sr and SiO₂−¹⁴³Nd/¹⁴⁴Nd isotope ratios in the volcanics suggest that fractional crystallization combined with minor assimilation was an important process within the collision zone.     

Secular variations of carbon and helium isotopes at Izu-Oshima Volcano, Japan

Secular variations in ¹³C/¹²C ratios and chemical compositions of gas samples from October 1986 to July 1992 are reported from a 92–95 °C steam well located about 3 km north of Mt. Mihara, an active volcano on Izu-Oshima Island, Japan. The δ¹³C value steeply increased from −2.97‰ (relative to PDB carbonate) in December 1986 to −1.15‰ in March 1988 and then gradually decreased to −1.75‰ in July 1992. Over the same period, the CO₂ content changed similarly with time, even though the experimental error is relatively large. These variations are consistent with helium isotope changes. Initially rapid and then slow enhancements of ³He/⁴He ratio, δ¹³C value and CO₂ content are invoked by violent eruptions of Izu-Oshima volcano from 15 November to 18 December 1986. After the eruptive activity, depletion of magmatic gas emission and subsequent mixing with crustal fluids in the hydrothermal system may produce the gradual decreases of ³He/⁴He ratio, δ¹³C value and CO₂ content. Taking into account the rates of these decreases, we suggest that helium and carbon isotope ratios will return to the situation of before the magmatic eruption within 15 years.     

Tracing effects of decalcification on solute sources in a shallow groundwater aquifer, NW Germany

δ⁸⁷Sr values and Ca/Sr ratios were employed to quantify solute inputs from atmospheric and lithogenic sources to a catchment in NW Germany. The aquifer consists primarily of unconsolidated Pleistocene eolian and fluviatile deposits predominated by >90% quartz sand. Accessory minerals include feldspar, glauconite, and mica, as well as disperse calcium carbonate in deeper levels. Decalcification of near-surface sediment induces groundwater pH values up to 4.4 that lead to enhanced silicate weathering. Consequently, low mineralized Ca–Na–Cl- and Ca–Cl-groundwater types are common in shallow depths, while in deeper located calcareous sediment Ca–HCO₃-type groundwater prevails. δ⁸⁷Sr values and Ca/Sr ratios of the dissolved pool range from 7.3 to −2.6 and 88 to 493, respectively. Positive δ⁸⁷Sr values and low Ca/Sr ratios indicate enhanced feldspar dissolution in shallow depths of less than 20 m below soil surface (BSS), while equilibrium with calcite governs negative δ⁸⁷Sr values and elevated Ca/Sr ratios in deep groundwater (>30 m BSS). Both positive and negative δ⁸⁷Sr values are evolved in intermediate depths (20–30 m BSS). For groundwater that is undersaturated with respect to calcite, atmospheric supplies range from 4% to 20%, while feldspar-weathering accounts for 8–26% and calcium carbonate for 62–90% of dissolved Sr²⁺. In contrast, more than 95% of Sr²⁺ is derived by calcium carbonate and less than 5% by feldspar dissolution in Ca–HCO₃-type groundwater. The surprisingly high content of carbonate-derived Sr²⁺ in groundwater of the decalcified portion of the aquifer may account for considerable contributions from Ca-containing fertilizers. Complementary tritium analyses show that equilibrium with calcite is restricted to old groundwater sources.