Temporal variation and the effect of rainfall on metals flux from the historic Beatson mine,Prince William Sound,Alaska, USA

Several abandoned Cu mines are located along the shore of Prince William Sound, AK, where the effect of mining-related discharge upon shoreline ecosystems is unknown. To determine the magnitude of this effect at the former Beatson mine, the largest Cu mine in the region and a Besshi-type massive sulfide ore deposit, trace metal concentration and flux were measured in surface run-off from remnant, mineralized workings and waste. Samples were collected from seepage waters; a remnant glory hole which is now a pit lake; a braided stream draining an area of mineralized rock, underground mine workings, and waste piles; and a background location upstream of the mine workings and mineralized rock. In the background stream pH averaged ∼7.3, specific conductivity (SC) was ∼40 μS/cm, and the aqueous components indicative of sulfide mineral weathering, SO₄ and trace metals, were at detection limits or lower. In the braided stream below the mine workings and waste piles, pH usually varied from 6.7 to 7.1, SC varied from 40 to 120 μS/cm, SO₄ had maximum concentrations of 32 mg/L, and the trace metals Cu, Ni, Pb, and Zn showed maximum total acid extractable concentrations of 186, 5.9, 6.2 and 343 μg/L, respectively.     

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments,Prince William Sound,Alaska, USA

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ? sphalerite < chalcopyrite ? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe–Al sulfate. The oxi dation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (∼3) and highest concentrations of base metals (to ∼25,000 μg/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO₄ are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe²⁺ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach–seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7–7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.     

Environmental geochemistry and quality assessment of mine water of Jharia coalfield,India

A long mining history and unscientific exploitation of Jharia coalfield caused many environmental problems including water resource depletion and contamination. A geochemical study of mine water in the Jharia coalfield has been undertaken to assess its quality and suitability for domestic, industrial and irrigation uses. For this purpose, 92 mine water samples collected from different mining areas of Jharia coalfield were analysed for pH, electrical conductivity (EC), major cations (Ca²⁺, Mg²⁺, Na⁺, K⁺), anions (F⁻, Cl⁻, HCO₃ ⁻, SO₄ ²⁻, NO₃ ⁻), dissolved silica (H₄SiO₄) and trace metals. The pH of the analysed mine water samples varied from 6.2 to 8.6, indicating mildly acidic to alkaline nature. Concentration of TDS varied from 437 to 1,593 mg L⁻¹ and spatial differences in TDS values reflect the variation in lithology, surface activities and hydrological regime prevailing in the region. SO₄ ²⁻ and HCO₃ ⁻ are dominant in the anion and Mg²⁺ and Ca²⁺ in the cation chemistry of mine water. High concentrations of SO₄ ²⁻ in the mine water of the area are attributed to the oxidative weathering of pyrites. Ca–Mg–SO₄ and Ca–Mg–HCO₃ are the dominant hydrochemical facies. The drinking water quality assessment indicates that number of mine water samples have high TDS, total hardness and SO₄ ²⁻ concentrations and needs treatment before its utilization. Concentrations of some trace metals (Fe, Mn, Ni, Pb) were also found to be above the desirable levels recommended for drinking water. The mine water is good to permissible quality and suitable for irrigation in most cases. However, higher salinity, residual sodium carbonate and Mg-ratio restrict its suitability for irrigation at some sites.     

The Diavik Waste Rock Project: Geochemical and microbiological characterization of low sulfide content large-scale waste rock test piles

Two experimental waste-rock piles (test piles), each 15 m in height × 60 m × 50 m, were constructed at the Diavik diamond mine in Northern Canada to study the behavior of low-sulfide content waste rock, with a similarly low acid-neutralization potential, in a continuous permafrost region. One test pile with an average of 0.035 wt.% S (<50 mm fraction; referred to as Type I) and a second test pile with an average of 0.053 wt.% S (<50 mm fraction; referred to as Type III) were constructed in 2006. The average carbon content in the <50 mm fraction of waste rock in the Type I test pile was 0.031 wt.% as C and in the Type III test pile was 0.030 wt.% as C. The NP:AP ratio, based on the arithmetic mean of particle-size weighted NP and AP values, for the Type I test pile was 12.2, suggesting this test pile was non-acid generating and for the Type III test pile was 2.2, suggesting an uncertain acid-generating potential. The Type I test pile maintained near-neutral pH for the 4-year duration of the study. Sulfate and dissolved metal concentrations were low, with the exception of Ni, Zn, Cd, and Co in the fourth year following construction. The pore water in the Type III test pile contained higher concentrations of SO₄²⁻ and dissolved metals, with a decrease in pH to <4.7 and an annual depletion of alkalinity. Maximum concentrations of dissolved metals (20 mg L⁻¹ Ni, 2.3 mg L⁻¹ Cu, 3.7 mg L⁻¹ Zn, 35 μg L⁻¹ Cd, and 3.8 mg L⁻¹ Co) corresponded to decreases in flow rate, which were observed at the end of each field season when the contribution of the total outflow from the central portion of the test pile was greatest. Bacteria were present each year in spite of annual freeze/thaw cycles. The microbial community within the Type I test pile included a population of neutrophilic S-oxidizing bacteria. Each year, changes in the water quality of the Type III test-pile effluent were accompanied by changes in the microbial populations. Populations of acidophilic S-oxidizing bacteria and Fe-oxidizing bacteria became more abundant as the pH decreased and internal test pile temperatures increased. Irrespective of the cold-climate conditions and low S content of the waste rock, the geochemical and microbiological results of this study are consistent with other acid mine drainage studies; indicating that a series of mineral dissolution–precipitation reactions controls pH and metal mobility, and transport is controlled by matrix-dominated flow and internal temperatures.     

Stream geochemistry, chemical weathering and CO2 consumption potential of andesitic terrains, Dominica, Lesser Antilles

Recent studies of chemical weathering of andesitic-dacitic material on high-standing islands (HSIs) have shown these terrains have some of the highest observed rates of chemical weathering and associated CO₂ consumption yet reported. However, the paucity of stream gauge data in many of these terrains has limited determination of chemical weathering product fluxes. In July 2006 and March 2008, stream water samples were collected and manual stream gauging was performed in watersheds throughout the volcanic island of Dominica in the Lesser Antilles. Distinct wet and dry season solute concentrations reveal the importance of seasonal variations on the weathering signal. A cluster analysis of the stream geochemical data shows the importance of parent material age on the overall delivery of solutes. Observed Ca:Na, HCO₃:Na and Mg:Na ratios suggest crystallinity of the parent material may also play an important role in determining weathering fluxes. From total dissolved solids concentrations and mean annual discharge calculations we calculate chemical weathering yields of (6-106 t km⁻² a⁻¹), which are similar to those previously determined for basalt terrains. Silicate fluxes (3.1-55.4 t km⁻² a⁻¹) and associated CO₂ consumption (190-1575 × 10³ mol km⁻² a⁻¹) determined from our study are among the highest determined to date. The calculated chemical fluxes from our study confirm the weathering potential of andesitic-dacitic terrains and that additional studies of these terrains are warranted.     

Controls of δS and δO in dissolved sulphate: Learning from a detailed survey in the Llobregat River (Spain)

The S and O isotopic composition of dissolved SO₄, used as a tracer for SO₄ sources, was applied to the water of the Llobregat River system (NE Spain). The survey was carried out at 30 sites where surface water was sampled on a monthly basis over a period of 2a. The concentration of dissolved SO₄ varied from 20 to 1575 mg L⁻¹. Sulphur isotopic compositions clustered in two populations: one – 93% of the samples – had positive values with a mode of +9‰; the other had negative values and a mode of −5‰. Data for δ¹⁸O_SO4 showed a mean value of +11‰, with no bi-modal distribution, though lower values of δ¹⁸O corresponded to samples with negative δ³⁴S. These values can not be explained solely by the contribution of bedrock SO₄ sources: that is, sulphide oxidation and the weathering of outcrops of sulphates, though numerous chemical sediments exist in the basin. Even in a river with a high concentration of natural sources of dissolved SO₄, such as the Llobregat River, the δ³⁴S values suggest that dissolved SO₄ is controlled by a complex mix of both natural and anthropogenic sources. The main anthropogenic sources in this basin are fertilizers, sewage, potash mine effluent and power plant emissions. Detailed river water sampling, together with the chemical and isotopic characterisation of the main anthropogenic inputs, allowed determination of the influence of redox processes, as well as identification of the contribution of natural and anthropogenic SO₄ sources and detection of spatial variations and seasonal changes among these sources. For instance, in the Llobregat River the input of fertilisers is well marked seasonally. Minimum values of δ³⁴S are reported during fertilization periods – from January to March – indicating a higher contribution of this source. The dual isotope approach, δ³⁴S and δ¹⁸O, is useful to better constrain the sources of SO₄. Moreover, in small-scale studies, where the inputs are well known and limited, the mixing models can be enhanced and the contribution of the different sources can be quantified to some extent.     

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.     

Predicting the impact of land use on the major element and nutrient fluxes in coastal Mediterranean rivers: The case of the Têt River (Southern France)

This study presents a detailed discrimination between the natural and anthropogenic sources of dissolved major elements in the Têt River, a typical small coastal river in the south of France. The main objectives were to quantify the materials that were released by human activities in the basin, and to determine the specific element inputs for the major land use forms. The dissolved material fluxes were estimated by weekly monitoring over a hydrological year (2000–2001) along the major water gauging stations, and the flux relationships were examined in the context of anthropogenic and natural basin characteristics as determined by a Geographical Information System (GIS). Intensive agricultural land use in the form of fruit tree cultures and vineyards has a strong control on the dissolved element fluxes in the river. Area specific element releases for these cultures are greatest for SO₄, with an estimated average of about 430 ± 18 keq km⁻² a⁻¹. This is ?11 times the natural SO₄ release by rock weathering. Also for K, NO₃, PO₄ and Mg, the specific releases were ?6 times the natural weathering rates (respectively about 44, 60, 4 and 265 keq km⁻² a⁻¹). Waste-waters are the other major source of anthropogenic elements in the river. They have an important role for the fluxes of inorganic P and N, but they are also a considerable source of Cl and Na to the river. For example, the average annual release of Cl is around 150 moles/inhabitant in the rural basin parts. Further downstream, however, where population density strongly increases, industrial effluents can enhance this value (>300 moles/inhabitant). The waste-waters contribute more than 70% of the dissolved inorganic N export to the sea, although their contribution to the average DOC export is almost negligible (3%).     

Silicate weathering in anoxic marine sediments

Two sediment cores retrieved at the northern slope of Sakhalin Island, Sea of Okhotsk, were analyzed for biogenic opal, organic carbon, carbonate, sulfur, major element concentrations, mineral contents, and dissolved substances including nutrients, sulfate, methane, major cations, humic substances, and total alkalinity. Down-core trends in mineral abundance suggest that plagioclase feldspars and other reactive silicate phases (olivine, pyroxene, volcanic ash) are transformed into smectite in the methanogenic sediment sections. The element ratios Na/Al, Mg/Al, and Ca/Al in the solid phase decrease with sediment depth indicating a loss of mobile cations with depth and producing a significant down-core increase in the chemical index of alteration. Pore waters separated from the sediment cores are highly enriched in dissolved magnesium, total alkalinity, humic substances, and boron. The high contents of dissolved organic carbon in the deeper methanogenic sediment sections (50-150 mg dm⁻³) may promote the dissolution of silicate phases through complexation of Al³⁺ and other structure-building cations. A non-steady state transport-reaction model was developed and applied to evaluate the down-core trends observed in the solid and dissolved phases. Dissolved Mg and total alkalinity were used to track the in-situ rates of marine silicate weathering since thermodynamic equilibrium calculations showed that these tracers are not affected by ion exchange processes with sediment surfaces. The modeling showed that silicate weathering is limited to the deeper methanogenic sediment section whereas reverse weathering was the dominant process in the overlying surface sediments. Depth-integrated rates of marine silicate weathering in methanogenic sediments derived from the model (81.4-99.2 mmol CO₂ m⁻² year⁻¹) are lower than the marine weathering rates calculated from the solid phase data (198-245 mmol CO₂ m⁻² year⁻¹) suggesting a decrease in marine weathering over time. The production of CO₂ through reverse weathering in surface sediments (4.22-15.0 mmol CO₂ m⁻² year⁻¹) is about one order of magnitude smaller than the weathering-induced CO₂ consumption in the underlying sediments. The evaluation of pore water data from other continental margin sites shows that silicate weathering is a common process in methanogenic sediments. The global rate of CO₂ consumption through marine silicate weathering estimated here as 5-20 Tmol CO₂ year⁻¹ is as high as the global rate of continental silicate weathering.     

Influence of freeze–thaw dynamics on internal geochemical evolution of low sulfide waste rock

Continuous monitoring of a 15 m high heavily instrumented experimental waste rock pile (0.053 wt.% S) since 2006 at the Diavik diamond mine in northern Canada provided a unique opportunity to study the evolution of fresh run-of-mine waste rock as it evolved over annual freeze–thaw cycles. Samples were collected from soil water solution samplers to measure pore water properties, from twelve 4 to 16 m² basal collection lysimeters to measure basal leachate properties in the region underlying the crest of the pile (the core), and from basal drains to measure aggregate total pile leachate properties. By 2012, monitoring of pore water geochemistry within the core structure of the test pile revealed an apparent steady state with respect to weathering geochemistry, represented by (i) a flush of pre-existing blasting residuals and applied tracers, (ii) declining pH, (iii) a stepwise progression and subsequent equilibrium with acid-neutralizing phases (depletion of available carbonates; equilibrium with respect to aluminum hydroxide phases and subsequent iron (III) hydroxide phases), and (iv) concordant release of SO₄, major cations (Ca, Mg, K, Na, Si), and trace metals (Al, Fe, Ni, Co, Cu, Zn). Distinct, high concentration ‘spring flushes’, characteristic of drainage in northern environments and primarily explained by a combination of fluid residence time and the build-up of oxidation products over the winter, were released from core drainage each season. Following the initial flush, the concentration of all dissolved constituents steadily declined, with distinct minimums prior to freeze-up. The opposite trend was observed in the cumulative pile drainage, in which early season leachate dominated by snowmelt and batter flow had low concentrations and late season leachate dominated by contributions from the core of the pile (indicated by season end merging of core and cumulative drainage geochemistry) had higher concentrations. Northern waste rock pile drainage geochemistry is strongly influenced by freeze–thaw cycling and varying core and batter subsystem contributions to total drainage. A comprehensive understanding of thermal cycling in waste rock piles is an important component of temporal predictions of drainage water composition based on up-scaling or reactive transport modeling.     

Geochemical behavior and speciation modeling of rare earth elements in acid drainages at Sarcheshmeh porphyry copper deposit,Kerman Province,Iran

Acid mine drainage is a major source of water pollution in the Sarcheshmeh porphyry copper mine area. The concentrations of heavy metals and rare earth elements (REEs) in the host rocks, natural waters and acid mine drainage (AMD) associated with mining and tailing impoundments are determined. Contrary to the solid samples, AMDs and impacted stream waters are enriched in middle rare earth elements (MREEs) and heavy rare earth elements (HREEs) relative to light rare earth elements (LREEs). This behavior suggests that REE probably fractionate during sulfide oxidation and acid generation and subsequent transport, so that MREE and HREE are preferentially enriched. Speciation modeling predict that the dominant dissolved REE inorganic species are Ln³⁺, Ln(SO₄)₂⁻, LnSO₄⁺, LnHCO₃²⁺, Ln(CO₃)₂⁻ and LnCO₃⁺. Compared to natural waters, Sarcheshmeh AMD is enriched in REEs and SO₄²⁻. High concentrations of SO₄²⁻ lead to the formation of stable LnSO₄⁺, thereby resulting in higher concentrations of REEs in AMD samples. The model indicates that LnSO₄⁺ is the dissolved form of REE in acid waters, while carbonate and dicarbonate complexes are the most abundant dissolved REE species in alkaline waters. The speciation calculations indicate that other factors besides complexation of the REE's, such as release of MREE from dissolution and/or desorption processes in soluble salts and poorly crystalline iron oxyhydroxy sulfates as well as dissolution of host rock MREE-bearing minerals control the dissolved REE concentrations and, hence, the MREE-enriched patterns of acid mine waters.     

Environmental geochemistry of Damodar River basin, east coast of India

 Water and bed sediment samples collected from the Damodar River and its tributaries were analysed to study elemental chemistry and suspended load characteristics of the river basin. Na and Ca are the dominant cations and HCO₃ is the dominant anion. The water chemistry of the Damodar River basin strongly reflects the dominance of continental weathering aided by atmospheric and anthropogenic activities in the catchment area. High concentrations of SO₄ and PO₄ at some sites indicate the mining and anthropogenic impact on water quality. The high concentration of dissolved silica, relatively high (Na+K)/TZ⁺ ratio (0.2–0.4) and low equivalent ratio of (Ca+Mg)/(Na+K) indicate that dissolved ions contribute significantly to the weathering of aluminosilicate minerals of crystalline rocks. The seasonal data show a minimum ionic concentration in the monsoon season, reflecting the influence of atmospheric precipitation on total dissolved solids contents. The suspended sediments show a positive correlation with discharge and both discharge and suspended load reach their maximum value during the monsoon season. Kaolinite is the mineral that is possibly in equilibrium with the water. This implies that the chemistry of the Damodar River water favours kaolinite formation. The concentration of heavy metals in the finer size fraction (<37 μ m) is significantly higher than the bulk composition. The geoaccumulation index values calculated for Fe, Mn, Zn, Ni and Cr are well below zero, suggesting that there is no pollution from these metals in Damodar River sediments. Received: 21 January 1998 · Accepted: 4 May 1998     

The CO2 system in rivers of the Australian Victorian Alps: CO2 evasion in relation to system metabolism and rock weathering on multi-annual time scales

The patterns of dissolved inorganic C (DIC) and aqueous CO₂ in rivers and estuaries sampled during summer and winter in the Australian Victorian Alps were examined. Together with historical (1978–1990) geochemical data, this study provides, for the first time, a multi-annual coverage of the linkage between CO₂ release via wetland evasion and CO₂ consumption via combined carbonate and aluminosilicate weathering. δ¹³C values imply that carbonate weathering contributes ∼36% of the DIC in the rivers although carbonates comprise less than 5% of the study area. Baseflow/interflow flushing of respired C3 plant detritus accounts for ∼50% and atmospheric precipitation accounts for ∼14% of the DIC. The influence of in river respiration and photosynthesis on the DIC concentrations is negligible. River waters are supersaturated with CO₂ and evade ∼27.7 × 10⁶ mol/km²/a to ∼70.9 × 10⁶ mol/km²/a CO₂ to the atmosphere with the highest values in the low runoff rivers. This is slightly higher than the global average reflecting higher gas transfer velocities due to high wind speeds. Evaded CO₂ is not balanced by CO₂ consumption via combined carbonate and aluminosilicate weathering which implies that chemical weathering does not significantly neutralize respiration derived H₂CO₃. The results of this study have implications for global assessments of chemical weathering yields in river systems draining passive margin terrains as high respiration derived DIC concentrations are not directly connected to high carbonate and aluminosilicate weathering rates.     

Major ion chemistry of the Yarlung Tsangpo-Brahmaputra river: Chemical weathering, erosion, and CO2 consumption in the southern Tibetan plateau and eastern syntaxis of the Himalaya

The Yarlung Tsangpo-Brahmaputra river drains a large portion of the Himalaya and southern Tibetan plateau, including the eastern Himalayan syntaxis, one of the most tectonically active regions on the globe. We measured the solute chemistry of 161 streams and major tributaries of the Tsangpo-Brahmaputra to examine the effect of tectonic, climatic, and geologic factors on chemical weathering rates. Specifically, we quantify chemical weathering fluxes and CO₂ consumption by silicate weathering in southern Tibet and the eastern syntaxis of the Himalaya, examine the major chemical weathering reactions in the tributaries of the Tsangpo-Brahmaputra, and determine the total weathering flux from carbonate and silicate weathering processes in this region. We show that high precipitation, rapid tectonic uplift, steep channel slopes, and high stream power generate high rates of chemical weathering in the eastern syntaxis. The total dissolved solids (TDS) flux from the this area is greater than 520 tons km⁻² yr⁻¹ and the silicate cation flux more than 34 tons km⁻² yr⁻¹. In total, chemical weathering in this area consumes 15.2 × 10⁵ mol CO₂ km⁻² yr⁻¹, which is twice the Brahmaputra average. These data show that 15-20% of the total CO₂ consumption by silicate weathering in the Brahmaputra catchment is derived from only 4% of the total land area of the basin. Hot springs and evaporite weathering provide significant contributions to dissolved Na⁺ and Cl⁻ fluxes throughout southern Tibet, comprising more than 50% of all Na⁺ in some stream systems. Carbonate weathering generates 80-90% of all dissolved Ca²⁺ and Mg²⁺ cations in much of the Yarlung Tsangpo catchment.     

The role of sulfur in chemical weathering and atmospheric CO2 fluxes: Evidence from major ions, δCDIC, and δSSO4 in rivers of the Canadian Cordillera

Water samples from the Fraser, Skeena and Nass River basins of the Canadian Cordillera were analyzed for dissolved major element concentrations (HCO₃⁻, SO₄²⁻, Cl⁻, Ca²⁺, Mg²⁺, K⁺, Na⁺), δ¹³C of dissolved inorganic carbon (δ¹³C_DIC), and δ³⁴S of dissolved sulfate (δ³⁴S_SO4) to quantify chemical weathering rates and exchanges of CO₂ between the atmosphere, hydrosphere, and lithosphere. Weathering rates of silicates and carbonates were determined from major element mass balance. Combining the major element mass balance with δ³⁴S_SO4 (−8.9 to 14.1‰_CDT) indicates sulfide oxidation (sulfuric acid production) and subsequent weathering of carbonate and to a lesser degree silicate minerals are important processes in the study area. We determine that on average, 81% of the riverine sulfate can be attributed to sulfide oxidation in the Cordilleran rivers, and that 25% of the total weathering cation flux can be attributed to carbonate and silicate dissolution by sulfuric acid. This result is validated by δ¹³C_DIC values (−9.8 to −3.7‰ _VPDB) which represents a mixture of DIC produced by the following weathering pathways: (i) carbonate dissolution by carbonic acid (−8.25‰) > (ii) silicate dissolution by carbonic acid (−17‰) ≈ (iii) carbonate dissolution by sulfuric acid derived from the oxidation of sulfides (coupled sulfide-carbonate weathering) (+0.5‰).δ³⁴S_SO4 is negatively correlated with δ¹³C_DIC in the Cordilleran rivers, which further supports the hypothesis that sulfuric acid produced by sulfide oxidation is primarily neutralized by carbonates, and that sulfide-carbonate weathering impacts the δ¹³C_DIC of rivers. The negative correlation between δ³⁴S_SO4 and δ¹³C_DIC is not observed in the Ottawa and St. Lawrence River basins. This suggests other factors such as landscape age (governed by tectonic uplift) and bedrock geology are important controls on regional sulfide oxidation rates, and therefore also on the magnitude of sulfide-carbonate weathering—i.e., it is more significant in tectonically active areas.Calculated DIC fluxes due to Ca and Mg silicate weathering by carbonic acid (38.3 × 10³ mol C · km⁻² · yr⁻¹) are similar in magnitude to DIC fluxes due to sulfide-carbonate weathering (18.5 × 10³ mol C · km⁻² · yr⁻¹). While Ca and Mg silicate weathering facilitates a transfer of atmospheric CO₂ to carbonate rocks, sulfide-carbonate weathering can liberate CO₂ from carbonate rocks to the atmosphere when sulfide oxidation exceeds sulfide deposition. This implies that in the Canadian Cordillera, sulfide-carbonate weathering can offset up to 48% of the current CO₂ drawdown by silicate weathering in the region.     

Hydrochemical characterization of acute acid mine drainage at Iron Duke mine, Mazowe, Zimbabwe

 Acid mine drainage (AMD) with a minimum pH of 0.52 was recorded at Iron Duke mine near Mazowe, Zimbabwe during an investigation of the environmental geochemistry of mine waters in the Greenstone Belts of Zimbabwe. Hydrochemical data for waters emanating from the Iron Duke waste-rock pile indicate their super-saturation with respect to Fe and SO₄ ^2–. Extremely high dissolved concentrations of Al, Zn, Cu, Co, Ni, V, Cr, Cd and As also prevail. Substantial losses of metals from solution occur within 400 m of the AMD source through the precipitation of crystalline sulphates, principally melanterite. Further downstream, hydrous oxide precipitation forms the dominant mechanism of metal attenuation in waters characteristically under-saturated with respect to Fe sulphates. Speciation and saturation index data generated using the equilibrium model WATEQ4F, suggest that such codes have broad utility for generic prediction of the mineralogical contraints on metal mobility in acute AMD systems. Major discrepancies between modelled and empirical hydrochemistries are, however, evident for super-saturated waters in which the kinetics of Fe precipitation are slow, and in which total ionic strengths markedly exceed their theoretical maximum. Received: 28 August 1998 · Accepted: 7 December 1998     

Redox potential (Eh) and anion effects of pyrite (FeS2) leaching at pH 1

Pyrite plays the central role in the environmental issue of acid rock drainage. Natural weathering of pyrite results in the release of sulphuric acid which can lead to further leaching of heavy and toxic metals from other associated minerals. Understanding how pyrite reacts in aqueous solution is critical to understanding the natural weathering processes undergone by this mineral. To this end an investigation of the effect of solution redox potential (Eh) and various anions on the rate of pyrite leaching under carefully controlled conditions has been undertaken.Leaching of pyrite has been shown to proceed significantly faster at solution Eh of 900 mV (SHE) than at 700 mV, at pH 1, for the leach media of HCl, H₂SO₄ and HClO₄. The predominant effect of Eh suggests electrochemical control of pyrite leaching with similar mechanism(s) at Eh of 700 and 900 mV albeit with different kinetics. Leach rates at 700 mV were found to decrease according to HClO₄ > HCl > H₂SO₄ while at 900 mV the leach rate order was HCl > HClO₄ > H₂SO₄. Solution Fe³⁺ activity is found to continually increase during all leaches; however, this is not accompanied by an increase in leach rate.Synchrotron based photoemission electron microscopy (PEEM) measurements showed a localised distribution of adsorbed and oxidised surface species highlighting that pyrite oxidation and leaching is a highly site specific process mediated by adsorption of oxidants onto specific surface sites. It appears that rates may be controlled, in part, by the propensity of acidic anions to bind to the surface, which varies according to , thus reducing the reactive or effective surface area. However, anions may also be involved in specific reactions with surface leach products. Stoichiometric dissolution data (Fe/S ratio), XPS and XRD data indicate that the highest leach rates (in HCl media at 900 mV Eh) correlate with relatively lower surface S abundance. Furthermore, there are indications that solution Cl⁻ assists oxidation especially at higher Eh through the prevention of surface S⁰ buildup at reactive surface sites.     

Chemical weathering, river geochemistry and atmospheric carbon fluxes from volcanic and ultramafic regions on Luzon Island, the Philippines

We investigated rates of chemical weathering of volcanic and ophiolitic rocks on Luzon Island, the Philippines. Luzon has a tropical climate and is volcanically and tectonically very active, all factors that should enhance chemical weathering. Seventy-five rivers and streams (10 draining ophiolites, 65 draining volcanic bedrock) and two volcanic hot springs were sampled and analyzed for major elements, alkalinity and ⁸⁷Sr/⁸⁶Sr. Cationic fluxes from the volcanic basins are dominated by Ca²⁺ and Mg²⁺ and dissolved silica concentrations are high (500-1900 μM). Silica concentrations in streams draining ophiolites are lower (400-900 μM), and the cationic charge is mostly Mg²⁺. The areally weighted average CO₂ export flux from our study area is 3.89 ± 0.21 × 10⁶ mol/km²/yr, or 5.99 ± 0.64 × 10⁶ mol/km²/yr from ophiolites and 3.58 ± 0.23 × 10⁶ mol/km²/yr from volcanic areas (uncertainty given as ±1 standard error, s.e.). This is ∼6-10 times higher than the current best estimate of areally averaged global CO₂ export by basalt chemical weathering and ∼2-3 times higher than the current best estimate of CO₂ export by basalt chemical weathering in the tropics. Extrapolating our findings to all tropical arcs, we estimate that around one tenth of all atmospheric carbon exported via silicate weathering to the oceans annually is processed in these environments, which amount to ∼1% of the global exorheic drainage area. Chemical weathering of volcanic terranes in the tropics appears to make a disproportionately large impact on the long-term carbon cycle.     

Sulfur speciation in natural hydrothermal waters, Iceland

The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pH_T was between 2.20 and 9.30 at the discharge temperature and the SO₄ and Cl concentrations were 0.020-52.7 and <0.01-10.0 mmol kg⁻¹, respectively. The analyses were carried out on-site within ∼10 min of sampling using ion chromatography (IC) for sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻) and polythionates (S_xO₆²⁻) and titration and/or colorimetry for total dissolved sulfide (S²⁻). Sulfite (SO₃²⁻) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S²⁻ were detected in all samples with concentrations of 0.02-52.7 mmol kg⁻¹ and <1-4100 μmol kg⁻¹, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394 μmol kg⁻¹ (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3 μmol kg⁻¹. Thiosulfate and SO₃²⁻ were not detected in <100 °C well waters and S₂O₃²⁻ was observed only at low concentrations (<1-8 μmol kg⁻¹) in ∼200 °C well waters. In alkaline and neutral pH hot springs, S₂O₃²⁻ was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (S_TOT). In steam-heated acid-sulfate waters, S₂O₃²⁻ was not a significant sulfur species. The results demonstrate that S₂O₃²⁻ and SO₃²⁻ do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ∼200-300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O₂, S²⁻ is degassed and oxidized to SO₃²⁻ and S₂O₃²⁻ and eventually to SO₄²⁻ at pH >8. In near-neutral hydrothermal waters the oxidation of S²⁻ and the interaction of S²⁻ and S⁰ resulting in the formation of S_x²⁻ are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO₄²⁻ and the sulfur chemistry of acid-sulfate pools was dominated by SO₄²⁻, which corresponded to >99% of S_TOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations.