Chemical composition of precipitation at Mt. Vesuvius and Vulcano Island,Italy: volcanological and environmental implications

Natural precipitation and water samples from passive devices were collected at Mt. Vesuvius and Vulcano Island, Italy, during the period 2004–2006, in order to investigate its possible interactions with fumarolic gases. Evidence of chemical reactions between fumarolic fluids and rain samples before and after its deposition into the sampling devices was found at Vulcano Island. Very low pH values (down to 2.5) and significant amounts of chlorine and sulfate (up to 22 mEq/l) were measured at sampling points located close to the fumarolic field. In contrast, anthropogenic contributions and/or dissolution of aerosols (both maritime and continental) influence the chemistry of rainwaters at Mt. Vesuvius, which show inter-annual variations that are highly consistent with those recorded at the coastal site at Vulcano Island. Chemistry of waters directly exposed to fumarolic fluids may then give useful information about its temporal evolution, holding the signal of the “maximum” chemical event occurred in the meanwhile. In addition, the observation of the health status of vegetation colonizing the immediate surroundings of the fumarolic fields, due to its strong dependence on the interactions with these fluids, may work as a possible biomarker of volcanic activity.     

A simple method for the determination of dissolved gases in natural waters. An application to thermal waters from Vulcano Island.

A new method for the determination of dissolved gas species in natural waters is presented. The method is suitable for field operations and ensures the preservation of the sample until analysis in the laboratory. This method is based on the equilibrium partition of gases between a liquid and a gaseous phase after the introduction of host gas. The host gas used depends on the gas species to be determined and on the technical features of the gas chromatograph. In this work pure Ar has been used. After shaking the sample for 5 min, a portion of gas was taken for gas chromatography analysis. From the concentration of gases in the gaseous phase and taking into account the partitioning coefficients of the various species, it is possible to derive the quantity of dissolved gases per litre of water and the partial pressures of the various gas species in equilibrium with water. This method has been applied to several samples of thermal water from Vulcano island. Helium and CO₂ partial pressures of analysed samples were appreciably higher than those typical of waters in equilibrium with the atmosphere, thus indicating processes of interaction between the volcanic gases and groundwaters.     

Aluminum chemistry: Fractionation,speciation, and mineral equilibria of soil interstitial waters of an alpine watershed,Front Range,Colorado

Soil interstitial waters and minerals were collected and analyzed to evaluate the influence of acid deposition on Al chemistry in the soil environment of the Green Lakes Valley Front Range, Colorado. The soil solutions were subjected to a series of batch Al experiments followed by computer modeling to separate the labile from the nonlabile Al, and to estimate the activity of Al³⁺. The Al solubility in the interstitial waters is complex and is controlled by organic solutes, H₄SiO₄, and pH. The pH and concentrations of SO²⁻₄ do not correlate with Al concentrations. The chemical equilibria of Al are controlled by amorphous aluminosilicate Al(OH)_3(1−x) SiO_2x. Studies of mineralogy and soil water chemistry provide a useful combination to evaluate and predict the chemical processes of a soil environment.     

Formation conditions of thermal springs in the Barguzin-Baikal area: Evidence from trace element and isotopic composition

Based on the relations between the chemical properties of elements, the formation conditions of thermal springs, and the geologic structure of the area, the main factors controlling the geochemistry of local fissure-vein waters were determined. Our results suggest that the most important factors are the temperature gradient and intensity of water exchange, which exert a fluctuating influence on the chemical composition of waters from different parts of the area. The chemical composition of hydrothermal waters provides insight into the geologic evolution of the region and conditions of water-rock interaction. It was shown that hydrochemical parameters can be used to refine the temperature of water heating, to rank springs by the duration of water-rock interaction, to establish the relative age and depth of faults that served as pathways for thermal water discharge, and to determine the geochemical conditions of water migration. The data reported in this paper demonstrate that fault-related mineralization formed during intense volcanic activity at the early stage of Baikal rift development affected the chemical composition of thermal springs.     

A simulation-based approach for estimating premining water quality: Red Mountain Creek,Colorado

Regulatory agencies are often charged with the task of setting site-specific numeric water quality standards for impaired streams. This task is particularly difficult for streams draining highly mineralized watersheds with past mining activity. Baseline water quality data obtained prior to mining are often non-existent and application of generic water quality standards developed for unmineralized watersheds is suspect given the geology of most watersheds affected by mining. Various approaches have been used to estimate premining conditions, but none of the existing approaches rigorously consider the physical and geochemical processes that ultimately determine instream water quality. An approach based on simulation modeling is therefore proposed herein. The approach utilizes synoptic data that provide spatially-detailed profiles of concentration, streamflow, and constituent load along the study reach. This field data set is used to calibrate a reactive stream transport model that considers the suite of physical and geochemical processes that affect constituent concentrations during instream transport. A key input to the model is the quality and quantity of waters entering the study reach. This input is based on chemical analyses available from synoptic sampling and observed increases in streamflow along the study reach. Given the calibrated model, additional simulations are conducted to estimate premining conditions. In these simulations, the chemistry of mining-affected sources is replaced with the chemistry of waters that are thought to be unaffected by mining (proximal, premining analogues). The resultant simulations provide estimates of premining water quality that reflect both the reduced loads that were present prior to mining and the processes that affect these loads as they are transported downstream. This simulation-based approach is demonstrated using data from Red Mountain Creek, Colorado, a small stream draining a heavily-mined watershed. Model application to the premining problem for Red Mountain Creek is based on limited field reconnaissance and chemical analyses; additional field work and analyses may be needed to develop definitive, quantitative estimates of premining water quality.     

On the problem of variability in the chemical composition of mud–volcanic waters: Evidence from the Yuzhno-Sakhalinsk mud volcano

The results of hydrogeochemical observations on the Yuzhno-Sakhalinsk mud volcano in 2010–2014 are considered. The chemical analysis of samples of mud–volcanic waters was carried out at various analytical centers, which is similar to the common situation where hydrochemical data for a volcano are obtained by different researchers. It is shown that the chemical composition of the mud–volcanic waters is relatively stable in time and space (for different gryphons of the volcano). This allows us to determine the characteristic range of hydrogeochemical indicators. For each year of observations, the coefficients of variation for the concentrations of Na, Mg, Ca, K, and HCO₃ mostly range from 10 to 30%. However, the concentrations analyzed in individual samples may differ significantly from each other. These natural variations are a likely source of errors in the interpretation of hydrochemical data. In addition, it is necessary to account for the specifics of mud–volcanic waters as an object of analytical chemical investigations.     

Groundwater and volcanoes: examples from the Azores archipelago

Groundwater at the Azores archipelago is a strategic resource for the freshwater supply. Freshwater, mineral and thermal water discharges occur in the archipelago, and especially at the Fogo and Furnas volcanoes (São Miguel). These discharges provide data for case studies of groundwater chemistry from volcanic monitoring due to the stable composition of the sampled waters. The mineral and thermal discharges are mainly of sodium bicarbonate types and present a large range of temperatures, from cold springs to waters at about 90 °C. Some boiling discharges have a sulfate-dominated composition, suggesting a steam-heating mechanism. Geochemical studies on these mineral and thermal waters began in the 19th century. Data gathered since these earlier studies provide a baseline for pH, temperature, CO₂ and major-element composition. Weekly measurements of pH and temperature also denote a rather stable behavior.     

Environmental impact of the acid fumarolic plume of a passively degassing volcano (Vulcano Island,Italy)

This paper investigates the role played by the fumarolic plume of a passive degassing volcano in the genesis of rock coatings (RC) and in the introduction and re-distribution of metals and trace elements in the surficial environment. At La Fossa active volcano (Vulcano Island) and in the surrounding environment RC develop owing to exposure of the ground surface to the volcanic acid plume produced by the passive degassing of La Fossa. Significant positive anomalies of a wide variety of metals and trace elements (including Bi, Ag, Se, Te, Sb, Pb, As, Cu, Tl and Cd) were observed either in distal and proximal RC. Most of these anomalies are interpreted to be the result of the transport and subsequent deposition of trace elements, likely to form volatile compounds, in the fumarolic plume. Two main processes seem to control the geochemistry of RC: one is represented by the leaching and subsequent deposition of elements from the proximal toward the distal RC; the other is the direct input of trace elements carried by the emitted volcanic aerosol. The fact that most of the trace elements (particularly Pb, As, Tl, Bi, Te, Se, Cd) enriched in the RC of Vulcano are highly toxic and potentially dangerous to health in high concentration, indicates that the atmospheric metal injection by the quiescently degassing La Fossa volcano together with the subsequent deposition and remobilization by means of surficial waters may represent an environmental hazard that should be taken into account in evaluating the potential impact of volcanic air pollution on human health.     

Genesis and distribution of mineral waters as a consequence of recent lithospheric dynamics: the Rhenish Massif,Central Europe

Three major, interdependent processes control the genesis and distribution of mineral and thermal waters in the Rhenish Massif, Central Europe: (a) Magmatic processes in the upper mantle provide most of the CO₂ to produce bicarbonate waters in shallow aquifers. (b) Extension of the brittle upper crust enables the ascent of sodium chloride waters. (c) Uplift and erosion shape the massif's relief, which determines the extent of flow systems and the distribution of thermal springs. The chemistry of mineral waters further depends on the aquifers' mineral composition. A comprehensive set of hydrological, chemical, tectonic and geophysical data on the Rhenish Massif has been compiled. It was used to classify the mineral waters and to map the spatial distribution of water properties. The composition of cuttings from several representative wells producing different water types shows that the hydrothermal alteration of the aquifer rocks consists mainly of kaolinization of chlorite and dissolution of feldspar. Numerical transport simulations favour two modes of groundwater flow: topography-driven flow and the pressure-driven ascent of basement brines along active faults. Thermal convection is less important.     

Major ion geochemistry of groundwaters from southern Nevada and eastern California, USA

The dissolved ionic constitutents of groundwaters are,in part,a recored of the minerals and rocks in aquifers through which the water has flowed.The chemical composition and association of these major ions in groundwaters have been used to trace groundwater flow paths and sources,In general,the chemical compostion of water in carbonate-rock aquifers in dominated by calcium,magnesium,and bicarbonate,whereas sodium,chloride,and sulfate can be dominant ions in the water that comes from volcanic aquifers or clay minerals.Since the 1990‘s,we have dealt with the geochemistry of groundwaters from more than 100 springs and wells in southern Nevada and eastrn california ,USA for major solutes and trace elements.This paper compiles the hydrochemical data of major ions of these groundwaters.Based on major ion geochemistry,groundwaters from southern Nevada and eastern California can be classified as carbonate aquifer water,volcanic aquifer water,and mixing water (either mixing of cabonate and volcanic aquifer waters or mixing with local recharges),Piper and stiff diagrams of major ions have graphically shown the general chemical characteristics,classification,and mixing relationships of groundwaters from southern Nevada and eastern California.     

Patterns in the transformation of the composition and properties of volcanogenic rocks in hydrothermal-magmatic systems of the Kuril-Kamchatka island arc

Hydrothermal-magmatic systems of the Kuril-Kamchatka island arc were formed in Neogene-Quaternary volcanic rocks. Acting on host rocks, thermal waters induced their alteration and transformation into hydrothermal-metasomatic rocks, such as propylites, secondary quartzites, zeolitic rocks, argillic rocks, opalites, quartz-adularia metasomatites, etc. The dynamics of changes in rock properties during the hydrothermal process depends on a number of factors, including the features of primary rocks, temperature, pressure and composition of thermal fluids, fluid phase, fluid pH, and duration of fluid-rock interaction. Deep high-temperature fluids cause consolidation and hardening of the rocks, an increase in deformational properties, and a decrease in porosity and permeability, regardless of fluid composition. The chemical composition and acidity-alkalinity of thermal fluids have a significant influence on the alteration of rock properties during low-temperature hydrothermal processes.     

Major ion chemistry of groundwater from perched-water bodies of the Azores (Portugal) volcanic archipelago

A dataset of major ion composition of 246 samples from cold-water springs discharging from perched-water bodies at volcanic islands (Azores archipelago, Portugal) reveal waters with low mineralization, which evolve due to two main geochemical processes: (1) seawater spraying and (2) dissolution of primary minerals of volcanic rocks. As a result, water facies range from Na–Cl to Na–HCO₃ type waters. The relationship between alkali, alkali–earth metals and HCO₃⁻ shows differences between waters discharging from perched-water bodies in basaltic rocks comparing to more evolved rocks of trachytic nature. The use of principal component analysis shows that water-rock interaction is limited, which is compatible with the geochemical observations and with the hydrogeological environment.     

The chemistry of geothermal waters in Iceland. II. Mineral equilibria and independent variables controlling water compositions

The major element chemistry of Icelandic geothermal waters is predictable provided two parameters are known. This follows from an attainment of, or a close approach to, an overall chemical equilibrium in the geothermal systems at temperatures as low as 50°C. It is considered that the geothermal system composition, temperature and kinetic factors determine which alteration minerals form. The system composition is not so much fixed by rock composition as by the rate of leaching of the various constituents from the fresh rock and the composition of inflowing water. The water chemistry is determined by the system composition and the external variables acting on the system. They include temperature and the mobility of chloride. Pressure, which theoretically should be regarded as an external variable, has insignificant effect on water compositions in the range (1–200 bars) occurring in the geothermal systems.     

中甸晚三叠世图姆沟组岩石化学与构造环境

本文对中甸东部晚三叠世图姆沟组深水浊积岩和弧火山岩、微量和稀土元素进行研究,投点多落入再旋回造山带物源区;微量和稀土元素与图解中多接近大陆岛弧区;常量元素分析与相关图解接近活动大陆边缘和大陆岛弧环境,与火山岩的大地构造环境具有相同的结论。图姆沟组为甘孜—理塘洋盆向西俯冲消减,中甸褶皱带东缘由被动大陆边缘转化为活动大陆边缘过程中形成的岛弧火山—沉积岩系。     

Arctic catchment as a sensitive indicator of the environmental changes: distribution and migration of metals (Svalbard)

Arctic regions experience metal pollution, despite their remote location, and the distribution and migration of those metals determine their potential impact on the local environment. Here, a High-Arctic catchment (Revelva, Svalbard) located remotely from human-induced pollution sources is studied with respect to the distribution and migration of chosen trace elements (Ag, Al, As, B, Ba, Bi, Ca, Cd, Co, Cr, Cu, Cs, Mo, Ni, Pb, Sb, Se, Sr, Tl, U, V and Zn) in surface waters. The metal concentrations fluctuated in 2010–2012 between 0.01 and 354 μg L^?1, the highest mean-weighted concentration noted for Sr (42.5 μg L^?1). The concentrations in the river water were likely influenced by both natural and human-activity-related processes. These factors can produce substances of the same chemical composition (e.g. carbon dioxide, sulphur dioxide and metals may be emitted both by a volcanic eruption and by industrial sources). Therefore, chemometric techniques were used in the current paper to distinguish the multiple sources of pollution in the Revelva catchment. The authors were seeking to determine whether there is indeed evidence for contamination, sufficient to cause environmental damage in polar region. As a result, it was shown that the long-range transport could play an important role in shaping the metal concentration profile of this Arctic tundra environment, capturing both the influence of volcanic eruptions within the region and the human activity in a range of distances from the study site.     

Origin of sulfur species in acid sulfate-chloride thermal waters,northeastern Japan

Acid sulfate-chloride thermal water samples collected together with fumarolic gases from various volcanic areas in northeastern Japan were studied chemically and isotogdically. δ³⁴S (COT) values of sulfate and hydrogen sulfide from these volcanic hot springs range from +4.0 to +31 and from ?15.0 to ?2.0% respectively, with δ³⁴S_ys value of +2.5 to +31. The δ³⁴S of the sulfate in the more saline waters tends to become smaller with increasing ratio of SO₄ to Cl, although the chemical and isotopic composition of acid thermal water within some areas may be altered by secondary processes during the discharge of the thermal waters. This trend can be explained by the reaction of the volcanic gases, having S/Cl of 4 ~ 7 and total sulfur of ~0% in δ³⁴S, with ground water at 200°C, and/or the removal of sulfide phase depleted in ³⁴S from the acid thermal water formed by the disproportionation of volcanic sulfur. The sulfur species in acid sulfate-chloride thermal water are shown to be volcanic exhalations.     

Environmental Controls on Groundwater Chemistry in an Offshore Island Aquifer: Fiesta Key, Florida

A field study was undertaken on the Florida Bay side of Fiesta Key, Florida, to identify the chemical characteristics of a previously unexplored offshore groundwater system and to define the critical parameters affecting groundwater movement and interaction with sediment pore fluids and bedrock. Emphasis was placed on the upper 2 meters of bedrock, where groundwater recharge and discharge potentials are maximized, along a 100 meter transect extending from the island margin. Bedrock cores were used to describe Pleistocene depositional textures, and were sampled at discrete depths to determine the extent of water-rock interaction. Piezometers installed into each core hole were used to monitor surface and ground water tide levels, and for the systematic collection of water samples for a large suite of chemical determinations.Aqueous chemical data indicate that these groundwaters are marine in origin, anoxic, and moderately hypersaline (S = 36–40). Exchange of bedrock pore fluids with overlying Bay waters is restricted by a layer of Holocene sediment and a discontinuous soilstone crust formed at the modern bedrock surface. Groundwater chemistry near the sediment/bedrock interface is marked by elevated concentrations of total alkalinity and Ca2+, and by significant Mg2+ depletion. These waters likely acquired their unusual chemistry by mixing between deeper groundwaters and overlying, early diagenetically altered, sediment porewaters. High alkalinity and calcium concentrations presumably result from the combination of the effects of aerobic metabolism, carbonate dissolution, and sulfate reduction. Mg-depletion most likely resulted from the precipitation of Mg-calcite. These unusual chemistries disappear by 2 m depth in the groundwater system, where Ca2+ and Mg2+ concentrations are similar to those expected for seawater under slightly hypersaline conditions.The Pleistocene bedrock contains low Mg, Sr, F, and P concentrations relative to the overlying unconsolidated Holocene carbonate sediments. This is consistent with the diagenetic recrystallization processes that the bedrock has undergone. Hydraulic conditions favor the net recharge of Florida Bay seawater to the groundwater system, but there are insufficient tide data to identify cyclical water exchange rates or groundwater flow patterns.     

The role of the crust in the magmatic evolution of the island of Lipari (Aeolian Islands,Italy)

Volcanic rocks on the island of Lipari show the entire range of Sr, Nd, Pb isotopic compositions displayed by other islands in the Aeolian archipelago. The rapid isotopic evolution of subaerial volcanic rocks on Lipari towards crustal values together with the appropriate isotopic composition of the neighbouring Calabrian crust (Serre) indicate that many geochemical characteristics observed in the lavas can be attributed to contamination and mixing with crustal materials and melts. Interpretation of the data is complicated by the fact that underplating onto the crust-mantle boundary and the specific lithologies present in the crustal section differ underneath each individual sector of the island. In the central and northern parts of the island, metapelitic rocks were incorporated to provide the more radiogenic Sr isotopic compositions of some lavas. The products from M. Guardia in the southern part of Lipari, where activity is restricted to the last 30–40 ka, bear geochemical similarities to the island of Vulcano, where it is proposed that considerable remobilization of the crust took place in the presence of mafic mantle-derived melts. On Lipari the petrogenetic processes of magma mixing and assimilation dominate over fractional crystallization, and the observed increase of K₂O over Na₂O can be correlated with contributions from metapelitic crustal lithologies. It is suggested that the variability in isotopic composition and the budget of alkalis (Na₂O versus K₂O) in the lavas can be explained by invoking a heat source from an intruding asthenospheric MORB-type mantle into a cooler lithospheric crust/mantle during the opening of the Tyrrhenian basin.     

南水北调中线水源地河水地球化学特征与流域侵蚀

丹江口水库及其上游流域是南水北调中线工程的水源地,本文讨论了水源地河流水化学与锶同位素(87Sr/86Sr)组成变化特征,目的在于了解水源地流域河流地表水溶质的物质来源以及岩石风化侵蚀过程和人为活动的影响。流域内河流水化学组成以Ca2+、HCO3-为主,Mg2+和SO42-次之,反映了碳酸盐岩风化溶解起控制作用的典型特征。水化学分析表明水源地河水受到工农业活动等人为因素的影响;河流87Sr/86Sr同位素地球化学研究表明,流域岩石风化输入至少存在三个不同端员(硅酸岩、石灰岩和白云岩)之间的混合。水源地流域内硅酸岩和碳酸岩的风化侵蚀速率分别为38.6和4.4 t/km2.a,总岩石风化侵蚀速率高于全球河流平均值。     

Naturally acidic surface and ground waters draining porphyry-related mineralized areas of the Southern Rocky Mountains,Colorado and New Mexico

Acidic, metal-rich waters produced by the oxidative weathering and resulting leaching of major and trace elements from pyritic rocks can adversely affect water quality in receiving streams and riparian ecosystems. Five study areas in the southern Rocky Mountains with naturally acidic waters associated with porphyry mineralization were studied to document variations in water chemistry and processes that control the chemical variations. Study areas include the Upper Animas River watershed, East Alpine Gulch, Mount Emmons, and Handcart Gulch in Colorado and the Red River in New Mexico. Although host-rock lithologies in all these areas range from Precambrian gneisses to Cretaceous sedimentary units to Tertiary volcanic complexes, the mineralization is Tertiary in age and associated with intermediate to felsic composition, porphyritic plutons. Pyrite is ubiquitous, ranging from ∼1 to >5 vol.%. Springs and headwater streams have pH values as low as 2.6, SO₄ up to 3700 mg/L and high dissolved metal concentrations (for example: Fe up to 400 mg/L; Cu up to 3.5 mg/L; and Zn up to 14.4 mg/L). Intensity of hydrothermal alteration and presence of sulfides are the primary controls of water chemistry of these naturally acidic waters. Subbasins underlain by intensely hydrothermally altered lithologies are poorly vegetated and quite susceptible to storm-induced surface runoff. Within the Red River study area, results from a storm runoff study documented downstream changes in river chemistry: pH decreased from 7.80 to 4.83, alkalinity decreased from 49.4 to <1 mg/L, SO₄ increased from 162 to 314 mg/L, dissolved Fe increased from to 0.011 to 0.596 mg/L, and dissolved Zn increased from 0.056 to 0.607 mg/L. Compared to mine drainage in the same study areas, the chemistry of naturally acidic waters tends to overlap but not reach the extreme concentrations of metals and acidity as some mine waters. The chemistry of waters draining these mineralized but unmined areas can be used to estimate premining conditions at sites with similar geologic and hydrologic conditions. For example, the US Geological Survey was asked to estimate premining ground-water chemistry at the Questa Mo mine, and the proximal analog approach was used because a mineralized but unmined area was located adjacent to the mine property. By comparing and contrasting water chemistry from different porphyry mineralized areas, this study not only documents the range in concentrations of constituents of interest but also provides insight into the primary controls of water chemistry.