Applied Geochemistry (v.24, #2)

Natural Low-pH Environments Unaffected by Human Activity by Robert G. Eppinger; Ron Fuge (189-190).

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid–sulfate waters by D. Kirk Nordstrom; R. Blaine McCleskey; James W. Ball (191-207).
Many waters sampled in Yellowstone National Park, both high-temperature (30–94 °C) and low-temperature (0–30 °C), are acid–sulfate type with pH values of 1–5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <±10%. When the charge imbalance was generally >±10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK 2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO4 concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high δ18O values (−10‰ to −3‰) and a δD vs. δ18O slope of 3, reflecting kinetic fractionation. Low SO4 concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid–sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone’s acid waters but have not been observed in acid rock drainage of the same pH.

Naturally acid waters from Copahue volcano, Argentina by J.C. Varekamp; A.P. Ouimette; S.W. Herman; K.S. Flynn; A. Bermudez; D. Delpino (208-220).
Volcanic acid sulfate–chloride brines form through absorption of volcanic vapors in shallow reservoirs of meteoric water. Reaction with surrounding volcanic rocks leads to partial neutralization of the fluids and precipitation of secondary minerals. Chemical data of such acid waters from Copahue volcano, Argentina, covering 8 years of observations, show evidence for changes in composition related to water rock interaction at depth prior to emergence of the fluids at the surface. The chemical composition changed dramatically during the 2000 eruption of Copahue, with enhanced concentrations and fluxes of Mg, Na, Fe and Al, followed in 2001 by rapidly declining concentrations and element fluxes. The subsequent 5 years saw more variable element ratios and strong depletions in K and Al. Most incompatible elements are released from the rock matrix stochiometrically, whereas some elements are enriched through vapor input from the magma (As, Pb, Zn). Most fluids have LREE enrichments relative to the rock matrix, but during periods of new magma intrusion the LREE enrichment decreases as does the magnitude of the negative Eu anomaly in the fluids. These observations are interpreted assuming early dissolution of plagioclase, olivine and volcanic glass that occurs during intrusion of new magma into the hydrothermal system. The high field strength elements are virtually immobile even in these hot acid fluids, with Nb and Ta more so than Hf and Zr. The mobility of U and Th in these fluids is comparable, at variance with Th behavior in neutral fluids. The local rivers and lakes of Copahue are fertilized by volcanic dissolved P, and most surface waters with pH < 3 have high levels of As. The acid fluids from Copahue may be surficial analogs for deep subduction fluids that evolve below zones of arc magma generation as well as for early Mars environments that are thought to have had large acid lakes.

Natural acid rock drainage associated with black shale in the Yukon Territory, Canada by Y.T. John Kwong; Gerry Whitley; Patrick Roach (221-231).
Investigated herein are water and sediment geochemistry, and metal attenuation processes associated with natural acid rock drainage originating from black shale formations in the Macmillan Pass area, Clear Lake prospect and Engineer Creek by the Dempster Highway in the Yukon Territory, Canada. The most metalliferous water having pH 3.0, 150 mg/L Zn, 39 mg/L Ni, 2.8 mg/L Cu and 9.1 mg/L As was found in a tributary stream of Engineer Creek with no known mineral deposits occurring in the vicinity. For all three study areas, the water and sediment geochemistry is significantly affected by the local lithology and prevailing metal attenuation processes. Despite their anomalous acidity and metal contents, the natural acid streams contribute only a small fraction of the contaminant loadings to the major water courses because of their low flows. Dilution, neutralization, sorption and co-precipitation are identified as the major mechanisms attenuating aqueous transport of potentially deleterious metals. However, microbial mediation in metal attenuation is also evident in low-flow systems. The wide variation of water and sediment geochemistry along a flow path renders the establishment of background metal values difficult. In assessing environmental impacts, it may be more practical to consider metal loadings on a watershed scale than to rely on a comparison with operationally defined background concentrations.

The Drenchwater shale-hosted Zn–Pb–Ag deposit and the immediate vicinity, on the northern flank of the Brooks Range in north-central Alaska, is an ideal example of a naturally low pH system. The two drainages, Drenchwater and False Wager Creeks, which bound the deposit, differ in their acidity and metal contents. Moderately acidic waters with elevated concentrations of metals (pH ⩾ 4.3, Zn ⩽ 1400 μg/L) in the Drenchwater Creek drainage basin are attributed to weathering of an exposed base-metal-rich massive sulfide occurrence. Stream sediment and water chemistry data collected from False Wager Creek suggest that an unexposed base-metal sulfide occurrence may account for the lower pH (2.7–3.1) and very metal-rich waters (up to 2600 μg/L Zn, ⩽ 260 μg/L Cu and ⩽89 μg/L Tl) collected at least 2 km upstream of known mineralized exposures. These more acidic conditions produce jarosite, schwertmannite and Fe-hydroxides commonly associated with acid-mine drainage. The high metal concentrations in some water samples from both streams naturally exceed Alaska state regulatory limits for freshwater aquatic life, affirming the importance of establishing base-line conditions in the event of human land development. The studies at the Drenchwater deposit demonstrate that poor water quality can be generated through entirely natural weathering of base-metal occurrences, and, possibly unmineralized black shale.

Low-pH waters discharging from submarine vents at Panarea Island (Aeolian Islands, southern Italy) after the 2002 gas blast: Origin of hydrothermal fluids and implications for volcanic surveillance by Franco Tassi; Bruno Capaccioni; Giorgio Caramanna; Daniele Cinti; Giordano Montegrossi; Luca Pizzino; Fedora Quattrocchi; Orlando Vaselli (246-254).
A geochemical survey of thermal waters collected from submarine vents at Panarea Island (Aeolian Islands, southern Italy) was carried out from December 2002 to March 2007, in order to investigate (i) the geochemical processes controlling the chemical composition of the hydrothermal fluids and (ii) the possible relations between the chemical features of the hydrothermal reservoir and the activity of the magmatic system. Compositional data of the thermal water samples were integrated in a hydrological conceptual model, which describes the formation of the vent fluid by mixing of seawater, seawater concentrated by boiling, and a deep, highly-saline end-member, whose composition is regulated by water-rock interactions at relatively high temperature and shows clear clues of magmatic-related inputs. The chemical composition of concentrated seawater was assumed to be represented by that of the water sample having the highest Mg content. The composition of the deep end-member was instead calculated by extrapolation assuming a zero-Mg end-member. The Na–K–Ca geothermometer, when applied to the thermal end-member composition, indicated an equilibrium temperature of approximately 300 °C, a temperature in agreement with the results obtained by gas-geothermometry.

Naturally acidic surface and ground waters draining porphyry-related mineralized areas of the Southern Rocky Mountains, Colorado and New Mexico by Philip L. Verplanck; D. Kirk Nordstrom; Dana J. Bove; Geoffrey S. Plumlee; Robert L. Runkel (255-267).
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.

Abundant shallow saline lakes on the Archean Yilgarn Craton in southern Western Australia exhibit a rare spectrum of geochemical conditions. Here the field geochemistry over three seasons (pH, salinity, and temperature), as well as major ions, trace elements, and H, O, and S stable isotopes of surface waters and shallow groundwaters from 59 ephemeral lakes in southern Western Australia (WA) are reported. Approximately 40% of the lakes and 84% of the measured groundwaters in WA are extremely acidic (pH < 4) and pHs are observed as low as 1.7. The salinity of lake waters and groundwaters ranges from rare freshwaters to common saline waters and brines with total dissolved solids >28%. The fluids are typically Na–Cl to Na–Mg–Cl–SO4 brines with variable yet locally high amounts of Ca, K, Al, Fe, Si, and Br. The acid brine fluid compositions are unusual. For example, in some fluids the amount of Al ≫ Ca , the amount of Br > K, and comparison of total S to SO 4 2 - values suggest the presence of other uncommon S-bearing species. Trends in δ18O and δ2H illustrate the separation between surface lake water and shallow groundwaters, and indicate the contribution of meteoric waters to the lakes. The chemical and isotopic compositions of these fluids indicate a spatially and temporally dynamic, yet regionally consistent, history of brine evolution that is fundamentally different from most other terrestrial closed basin brines. The WA lake brines do not evolve from surface evaporation of dilute inflow waters, but rather are fed by highly evolved regionally acid saline groundwaters. The lake waters then diversify with locally varying surface and near-surface processes such as meteoric dilution by flooding, evapoconcentration, mineral precipitation and dissolution, and fluid mixing. The WA lake waters and groundwaters are somewhat similar to those in an entirely different geologic setting in northeastern Victoria, illustrating the potential for different geochemical pathways to lead to the formation of similar lacustrine acid brines. Although these types of environments are rare in modern settings, ancient ephemeral acid saline lake deposits have been recognized in the geologic record on Earth and on Mars, indicating that natural evolution of acid saline waters may be more ubiquitous than previously recognized.

There is now evidence that naturally occurring acid–water is more abundant than previously thought and that it has been important in the geologic past. Understanding the processes leading to the formation of such systems is required to appreciate the role of acid systems in geologic processes and to develop indicators for recognizing the geologic/environmental importance of these systems in the past. This paper characterizes the hydrogeology, hydrogeochemistry, microbial biogeochemistry and landscape attributes of acid–groundwater surface water systems in Australia with an emphasis on a well studied playa-lake system, Lake Tyrrell, Murray Valley. A model for the origin of these acid brines is presented and the importance of acid-brine producing systems is speculated upon. Data include porewater and groundwater geochemical measurements (collected during a 10 day field campaign) and results from geochemical modeling and graphics (e.g., Piper diagrams and xy plots of seawater evaporation trajectories). Key characteristics of the system are (1) aquifer materials have low acid buffering capacities, (2) saline groundwater flowing onto playa surfaces is an oxic, H2SO4 solution, (3) authigenic minerals include combinations of jarosite [KFe3(SO4)2(OH)6], alunite [KAl3(SO4)2(OH)6] and Fe oxides that can form as evaporite minerals, (4) a source for solutes can be marine aerosols and (5) the formation of ironstones. Groundwater acidification by various processes including sulfide oxidation and ferrolysis, and at many different times, are the unique aspects for evolution of these acid brines and they can be considered another end member of the Eugster–Jones–Hardie model for the evolution of brines in closed basins. Acid–hypersaline groundwater and playa systems such as Lake Tyrrell may be an example of expected changes in the hydrogeochemistry of terrestrial water during late-stage continental denudation under arid conditions. Historically these systems may have been integral to the formation of opal, bauxite, some low temperature ore deposits, of authigenic K-feldspars, and continental redbeds. Natural acid saline systems, such as those in Australia, may also be representative of acid saline systems on Mars.

Features of acid–saline systems of Southern Australia by Bruce L. Dickson; Angela M. Giblin (297-302).
The discovery of layered, SO4-rich sediments on the Meridiani Planum on Mars has focused attention on understanding the formation of acid–saline lakes. Many salt lakes have formed in southern Australia where regional groundwaters are characterized by acidity and high salinity and show features that might be expected in the Meridiani sediments. Many (but not all) of the acid–saline Australian groundwaters are found where underlying Tertiary sediments are sulfide-rich. When waters from the formations come to the surface or interact with oxidised meteoric water, acid groundwaters result. In this paper examples of such waters around Lake Tyrrell, Victoria, and Lake Dey-Dey, South Australia, are reviewed. The acid–saline groundwaters typically have dissolved solids of 30–60 g/L and pH commonly <4.5. Many contain high concentrations of Fe and other metals, leached from local sediments. The combination of acidity and salinity also releases Ra. Around salt-lakes, these acidic waters often emerge at the surface in marginal spring zones where the low density (ρ  ∼ 1.04) regional water flows out over the denser (ρ  ∼ 1.16) lake brines. In the spring zones examined, large amounts of Fe are commonly precipitated. In a few places minerals of the alunite-jarosite family are formed which can trap many other metals, including Ra. The studied groundwater systems were discovered by U exploration programs following up radiometric anomalies related to this Ra. Evaporation concentrates the lesser soluble salts (gypsum and some halite) on the surface of the lakes. The lake brines contain most of the more soluble salts and form a column within the porous sediments which is held in place by hydrostatic forces around the salt-lake. These brines are near-neutral in pH.These observations are in contrast to the jarosite-bearing aeolianites found on the Meridiani Planum, Mars. These have an almost homogeneous distribution of Fe oxides and jarosite, with little separation of salts with different solubilities (CaSO4 and MgSO4) or differential separation of elements with differing solubility (K, Na, Ti, Cr). Thus, it is considered unlikely that groundwaters or evaporative salt-lake systems, as found on earth, were involved. Instead, these features point to a water-poor system with local alteration and very little mobilization of elements.

Characterization of hydrothermally generated oil from the Uzon caldera, Kamchatka by Bernd R.T. Simoneit; David W. Deamer; Vladimir Kompanichenko (303-309).
This paper reports the analyses of unusual oils that accumulate in the Uzon Caldera, situated in the central volcanic region of Kamchatka, Russia. Gas chromatography–mass spectrometry (GC–MS) was used to determine the primary constituents, and the 13C and 14C compositions provided information about the potential source and age of the oils. The 14C ages determined are 1030 ± 40 a BP (measured) or 940 ± 40 a BP (conventional). The δ 13C value is −30.6‰ versus the PDB standard, a value consistent with a biological origin. The nearly contemporary age of the C content indicates a geologically recent origin from biogenic detritus and not by synthesis from mantle C. The biogenic origin is supported by the presence of sterane and hopane biomarkers and the δ 13C value of the bulk oil. The overall compositions of the oils indicate that they are derived from rapid hydrothermal alteration of algal/bacterial mat detritus buried by volcanic ashfall deposits of the Uzon Caldera. The oils represent the youngest hydrothermal petroleum reported to date.

An analytical expression that evaluates the effect of pH and the redox potential (E) on Pu-colloid association was studied on a model basis. It includes surface complexation with one type of surface site and its formulation leads to a distribution coefficient (K d) as a function of the pH (hydrolysis) and E (redox sensitive species). The formulation also considers the values of the stability and hydrolysis constants for all species present in solution and associated at the surface. Correlations between hydrolysis and surface complexation constants reported in the literature have been applied systematically to evaluate sorption of all species for each colloid system. The presence of ligands in solution was also taken into account. The model was applied to study the association of Pu onto colloids coated with AlOH, FeOH or SiOH groups in the presence and in the absence of carbonates in solution. The tests performed with the model suggest that the oxidation of Pu(III) to Pu(IV) has the potential to increase sorption, as demonstrated by the increased K d values. Under natural conditions Pu may be present at oxidation states of (III)--(VI), and the effect of redox potential is significant because of the differences in the sorption of each oxidation state. When carbonates are present in the solution, the calculated values of distribution coefficient were lower than those calculated in the absence of carbonates, particularly in the case of Pu(VI). The K d values obtained with the developed model are compared with experimental values reported for the sorption of Pu onto colloids. This model can equally be applied to study the sorption of other redox sensitive elements.

Stable isotope characterization of fluids from the Lake Chany complex, western Siberia, Russian Federation by C. Mizota; H. Doi; E. Kikuchi; S. Shikano; T. Kakegawa; N. Yurlova; A.K. Yurlov (319-327).
The Lake Chany complex and nearby lakes in western Siberia (Russian Federation) were studied to constrain the S cycle in these terrestrial lake environments. Surface water chemistry was characterized by Na–SO4–Cl composition, comparable to other inland basins in semi-arid climatic zones associated with marine evaporite-bearing formations at depth. Dissolved sulfates showed elevated δ 34S (up to +32.3‰). These values are quite distinct from those in similar saline lakes in northern Kazakhstan, the Aral Sea, Lake Barhashi, and a gypsum deposit in the Altai Mountains. The localized distribution of such a unique S isotopic signature in dissolved SO4 negates both aeolian and catastrophic flooding hypotheses previously suggested for the genesis of the dissolved salts. The probable source of the dissolved SO4 in Lake Chany basin is inherited from hidden saline groundwaters (whose location and origins remain unclear) from eastern Paleozoic ranges with Upper Devonian formations with heavy S isotope values. Post-depositional enrichment of heavy S in the dissolved SO4 from saline sediments may be caused by local activity of SO4-reducing bacteria under the ambient supply of electron donors (dissolved river load organic matter and decaying bacterial mats) in the lake complex. Such microbial processes can remove up to ca. 60% of SO4 from the system. Extensive and intensive evaporation of lake fluids, ca. 40%, was indicated by the progressive enrichment of δ 18O values in meteoric water samples collected along the river and lake system. This evaporation process compensates the microbial loss of SO4 dissolved in the incoming river water.

Temporal variations in the concentration and N isotopic ratios of inorganic N (NH4– and NO3–N) as affected by the soil temperature regime together with the input of bird excreta were analyzed in a sedentary soil under a dense colony (1.6 nests/m2) of breeding Black-tailed Gulls (Larus crassirostris: a ground-nesting seabird). Surface soil samples were taken monthly from mid-March to late July 2005 from Kabushima Island, Hachinohe, northeastern Japan. The spatial concentration of inorganic N in the soils varied considerably on all sampling dates. There may be a statistically significant trend, showing increased NH4–N content from settlement up to early June when the input of fecal N attains its maximum, and then decreases towards the end of breeding activity (early August). Abundant NO3–N was observed in all soils, particularly in the later stage of breeding (up to 3800 mg-N/kg dry soil), refuting earlier claims that nitrification is unimportant in the soils. δ15N values of NH4 in the soils showed unusually high values up to +51‰, reflecting N isotope fractionation due to volatilization of NH3 during the mineralization. Mean δ15N values of the monthly collected totals of NH4 and NO3 were not significantly different at the 5% level based on ANOVA and significant differences were observed only among the three means of NO3–N collected in mid-March (settlement of colony: δ15N = −0.2 ± 3.5‰) and late July (later stages of breeding: δ15N = +22.1 ± 7.0‰, +23.3 ± 7.8‰) at the 1% and 5% levels by t-test, respectively. Such an observation of significantly increased δ15N values for NO3–N in soils from the fledgling stage indicates the integration of denitrification coupled with nitrification under a limited supply of fecal N.

Natural and constructed clay liners are routinely used to contain waste and wastewater. The impact of acidic solutions on the geochemistry and mineralogy of clays has been widely investigated in relation to acid mine drainage systems at pH > 1.0. The impact of H2SO4 leachate characterized by pH < 1.0 and potentially negative pH values on the geochemistry and mineralogy of clays is, however, not clear. Thus, laboratory batch experiments were conducted on three natural clay samples with different mass ratios of smectite, illite and kaolinite to investigate the impact of H2SO4 on the geochemistry and mineralogy of aluminosilicates from pH 5.0 to −3.0. Batch testing was conducted at seven pH treatments (5.0, 3.0, 1.0, 0.0, −1.0, −2.0 and −3.0) using standardized H2SO4 solutions for four exposure periods (14, 90, 180, and 365 d). Aqueous geochemical and XRD analyses showed: increased dissolution of aluminosilicates with decreasing pH and increasing exposure period, that smectite was more susceptible to dissolution than illite and kaolinite, precipitation of an amorphous silica phase occurred at pH ⩽ 0.0, and anhydrite precipitated in Ca-rich clays at pH ⩽ −1.0. In addition, global dissolution rates were calculated for the clays and showed good agreement to literature smectite, illite and kaolinite dissolution rates, which suggests global dissolution rates for complex clays could be determined from monomineralic studies. A stepwise conceptual model of the impact of H2SO4 on aluminosilicate geochemistry and mineralogy between pH 5.0 and −3.0 is proposed.

Aqueous and solid phase arsenic speciation in the sediments of a contaminated wetland and riverbed by N.K. Blute; J.A. Jay; C.H. Swartz; D.J. Brabander; H.F. Hemond (346-358).
Mobility of As in the environment is controlled by its association with solid phases through adsorption and co-precipitation. To elucidate the mobilization potential of As deposited in wetland and riverbed sediments of the Wells G & H wetland in Woburn, MA as the result of decades of industrial activity, As retention mechanisms were inferred from aqueous and solid phase geochemical measurements of sediment cores. Testing included a sequential extraction method designed for and standard-tested with As phases and pE/pH equilibrium modeling. The uppermost sediments in the Wells G & H wetland contain elevated concentrations of both dissolved and solid phase As (up to 2,000 μg/L and 15,000 μg/g, respectively) and a maximum concentration between 30 and 40 cm depth. Measurements obtained in this study suggested that As in the wetland sediments was predominantly adsorbed, likely onto amorphous Fe (hydr)oxide phases and mixed valence Fe phases. In the riverbed sediments, however, a relatively greater proportion of the solid As was associated with more reduced and crystalline phases, and adsorbed As was more likely associated with Al oxide or secondary reduced Fe phases. pH–pe modeling of the Fe–As–S system was consistent with observations. The association of As with more oxidized phases in the wetland compared with the riverbed sediments may result from a combination of plant activities, including evapotranspiration-driven water table depression and/or root oxygenation.