Kinetic modelling of geochemical processes at the Aitik mining waste rock site in northern Sweden

A steady-state geochemical model has been developed to study water-rock interactions controlling metal release from waste rock heaps at the Aitik Cu mine in northern Sweden. The Cu release in drainage waters from the site is of environmental concern. The waste rock heaps are treated as single completely mixed flow-through reactors. The geochemical model includes kinetices of sulphide and primary silicate mineral weathering, heterogeneous equilibrium with secondary mineral phases and speciation equilibrium. Field monitoring of drainage water composition provides a basis for evaluation of model performance.The relative rate of oxidative weathering of sulphides and dissolution of primary silicate minerals, using published kinetic data, are consistent with net proton and base cation fluxes at the site. The overall rate of Fe²⁺ oxidation within the heap is three orders of magnitude faster than that which could be explained by surface-catalysed reaction kinetics. This suggests significant activity of iron-oxidizing bacteria. The absolute weathering rates of sulphides and silicate minerals, normalized to a measured BET surface area, are approximately two orders of magnitude lower at field scale than published rates from laboratory experiments. Because of the relative absence of carbonate minerals, the weathering of biotite and plagioclase feldspar are important sources of alkalinity.     

The Diavik Waste Rock Project: Particle size distribution and sulfur characteristics of low-sulfide waste rock

Three large-scale instrumented waste rock piles were constructed at the Diavik Diamond Mine in the Northwest Territories, Canada. These experimental waste rock piles (test piles) are 15 m high and are part of an integrated field and laboratory research program to characterize and compare low-sulfide waste rock and drainage at various scales. During test pile construction, samples of the <50 mm fraction of waste rock were collected from two types of waste rock that are segregated during mining operations based on S content. The samples were analyzed for S content and particle size distribution. One test pile contained waste rock with an average of 0.035 wt.% S in the <50 mm fraction, within the operational S target of <0.04 wt.% S for the lower S waste rock type. The second test pile contained waste rock with an average of 0.053 wt.% S in the <50 mm fraction, lower than the operational S target of >0.08 wt.% S for the higher S waste rock type. The third test pile has a low permeability till layer and a low sulfide waste rock thermal layer covering a core of waste rock with average 0.082 wt.% S in the <50 mm fraction, which is within the operational S target of >0.08 wt.% S for the higher S waste rock. Particle size distributions for the lower and higher S waste rock are similar, but the higher S waste rock has a higher proportion of fine-grained particles. Sulfur determinations for discrete particle sizes of the <50 mm fraction illustrate higher S concentrations in smaller particles for both the lower S waste rock and the higher S waste rock. Similarly, S concentrations calculated for the >10 m scale, from composite blast hole cuttings, are lower than those calculated for the <50 mm scale. Acid–base accounting using standard methods and site-specific mineralogical information was used to calculate the ratio of neutralization potential to acid generating potential. A comparison of calculation approaches to pH and alkalinity data from humidity cell and test pile effluent suggest that ratios are very sensitive to the calculation method. The preferred calculation method was selected by comparing calculation results to pH and alkalinity data from humidity cell effluent collected over 95 weeks and test pile effluent collected over five field seasons. The preferred acid–base accounting values were obtained by calculating the average neutralization potential divided by the average acid potential of a sample set. This approach indicates that waste rock with >0.05 wt.% S is of uncertain acid-generating potential and effluent data indicate this waste rock generates acidic effluent; whereas lower S waste rock does not produce acidic effluent, consistent with the acid–base accounting predictions.     

The ubiquitous nature of accessory calcite in granitoid rocks: Implications for weathering, solute evolution, and petrogenesis

Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg⁻¹ (mean = 2.52 g kg⁻¹). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and ⁸⁷Sr/⁸⁶Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO₂ in DI water for 75 d at 25°C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and ⁸⁷Sr/⁸⁶Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and ⁸⁷Sr/⁸⁶Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO₂ fugacities, calcite is a stable phase at temperatures of 400 to 700°C.     

Environmental geochemistry of the derelict Webbs Consols mine,New South Wales,Australia

Small-scale mining and mineral processing at the Webbs Consols polymetallic PbZnAg deposit in northern New South Wales, Australia has caused a significant environmental impact on streams, soils and vegetation. Unconfined waste rock dumps and tailings dams are the source of the problems. The partly oxidised sulphidic mine wastes contain abundant sulphides (arsenopyrite, sphalerite, galena) and oxidation products (scorodite, anglesite, smectite, Fe-oxyhydroxides), and possess extreme As and Pb (wt% levels) and elevated Ag, Cd, Cu, Sb and Zn values. Contemporary sulphide oxidation, hardpan formation, crystallisation of mineral efflorescences and acid mine drainage generation occur within the waste repositories. Acid seepages (pH 1.9–6.0) from waste dumps, tailings dams and mine workings display extreme As, Pb and Zn and elevated Cd, Cu and Sb contents. Drainage from the area is by the strongly contaminated Webbs Consols Creek and although this stream joins and is diluted by the much larger Severn River, contamination of water and stream sediments in the latter is evident for 1–5 km, and 12 km respectively, downstream of the mine site. The pronounced contamination of local and regional soils and sediments, despite the relatively small scale of the former operation, is due to the high metal tenor of abandoned waste material and the scarcity of neutralising minerals. Any rehabilitation plan of the site should include the relocation of waste materials to higher ground and capping, with only partial neutralisation of the waste to pH 4–5 in order to limit potential dissolution of scorodite and mobilisation of As into seepages and stream waters.     

Phosphate amendment of metalliferous waste rocks, Century Pb-Zn mine, Australia: Laboratory and field trials

The aim of the study was to determine whether the application of phosphate compounds (phosphorite rock, phosphate fertilizer) to polyminerallic waste rocks can inhibit sulfide oxidation and metal mobility (Cu, Pb, Zn, Cd, Ni, Mn, Mg). Waste rocks comprised sulfidic carbonaceous shales and were sourced from the Century Pb-Zn mine, NW Queensland, Australia. The acid producing, Pb-Zn rich rocks consisted of major quartz, muscovite/illite, dolomite, siderite and kaolinite as well as smaller amounts of sulfide minerals (e.g. galena, sphalerite, pyrite). Laboratory leach experiments were conducted on finely granulated phosphate-treated waste rocks (>2 to <30 mm) over 13 weeks, whereas phosphate amendment of coarsely granulated waste rocks (sand to boulder size) was investigated using heap leach piles at the mine site over an 11 months period. Results of the laboratory experiments demonstrate that the treatment of finely granulated waste rocks with phosphorite rock produced leachates with near-neutral pH values due to calcite dissolution. This in turn did not allow the leaching of apatite, formation of secondary phosphate phases and phosphate stabilization to occur. Metal mobility in these amended wastes was restricted by the dissolution of calcite and the resultant near-neutral pH conditions. By contrast, the application of the water-soluble phosphate fertilizer MKP (KH₂PO₄) to polyminerallic sulfidic waste rocks during the short-term laboratory experiments led to the formation of phosphate coatings and precipitates and inhibited acid and metal release (Cd, Mn, Ni, Pb, Zn). At least in the short term, the application of phosphate fertilizers proved to be an effective method. However, results of the long-term field trials demonstrate that coarsely granulated waste rocks were not coated by secondary phosphate phases and that amendment by phosphorite rock or superphosphate fertilizer did not improve leachate quality compared to the unamended waste. Thus, phosphate stabilization appears ineffective in suppressing oxidation of sulfides in coarsely granulated mine wastes.     

Particle size distribution and dissolution properties of metals in cyclone fly ash

The particles in the examined cyclone fly ash were all smaller than 0.25 mm. in diameter, and particles smaller than 0.075 mm. in diameter accounted for 88.4 % of the ash weight. This result indicates that cyclone fly ash consists of particles with a small diameter. The metals in the cyclone fly ash were enriched in small particles. The highest concentrations for zinc, copper, lead, cadmium and molybdenum in the cyclone fly ash were found in the smallest particle size fraction (< 0.075 mm.) and for Barium, chromium, nickel, Vanadium and Cobalt in the second to smallest particle size fraction (0.075-0.125 mm.). From an environmental and toxicological standpoint, the smallest particles are of the greatest concern when ash is handed at landfill disposal sites (transport and disposal especially in stormy weather conditions), and some studies have reported risks to workers from prolonged exposure to ash. The results of the comparison of various dissolution methods for metals showed that the digestion procedures with nitric acid alone (USEPA 3051) or with a mixture of nitric acid + hydrogen peroxide (USEPA 3050B) slightly underestimated the metal concentrations in the cyclone fly ash. Although the use of hydrofluoric acid is often necessary for the determination of a number of elements associated with siliceous minerals, its use can result in loss of trace elements during dissolution.     

On the neutralization of acid rock drainage by carbonate and silicate minerals

The net result of acid-generating and-neutralizing reactions within mining wastes is termed acid rock drainage (ARD). The oxidation of sulfide minerals is the major contributor to acid generation. Dissolution and alteration of various minerals can contribute to the neutralization of acid. Definitions of alkalinity, acidity, and buffer capacity are reviewed, and a detailed discussion of the dissolution and neutralizing capacity of carbonate and silicate minerals related to equilibium conditions, dissolution mechanism, and kinetics is provided. Factors that determine neutralization rate by carbonate and silicate minerals include: pH, P_{CO 2}, equilibrium conditions, temperature, mineral composition and structure, redox conditions, and the presence of foreign ions. Similar factors affect sulfide oxidation. Comparison of rates shows sulfides react fastest, followed by carbonates and silicates. The differences in the reaction mechanisms and kinetics of neutralization have important implications in the prediction, control, and regulation of ARD. Current static and kinetic prediction methods upon which mine permitting, ARD control, and mine closure plans are based do not consider sample mineralogy or the kinetics of the acid-generating and-neutralizing reactions. Erroneous test interpretations and predictions can result. The importance of considering mineralogy for site-specific interpretation is highlighted. Uncertainty in prediction leads to difficulties for the mine operator in developing satisfactory and cost-effective control and remediation measures. Thus, the application of regulations and guidelines for waste management planning need to beflexible.     

Stability and leaching of cobalt smelter fly ash

The leaching behaviour of fly ash from a Co smelter situated in the Zambian Copperbelt was studied as a function of pH (5–12) using the pH-static leaching test (CEN/TS 14997). Various experimental time intervals (48 h and 168 h) were evaluated. The leaching results were combined with the ORCHESTRA modelling framework and a detailed mineralogical investigation was performed on the original FA and leached solid residues. The largest amounts of Co, Cu, Pb and Zn were leached at pH 5, generally with the lowest concentrations between pH 9 and 11 and slightly increased concentrations at pH 12. For most elements, the released concentrations were very similar after 48 h and 168 h, indicating near-equilibrium conditions in the system. Calcite, clinopyroxenes, quartz and amorphous phases predominated in the fly ash. Various metallic sulfides, alloys and the presence of Cu, Co and Zn in silicates and glass were detected using SEM/EDS and/or TEM/EDS. The leaching of metals was mainly attributed to the dissolution of metallic particles. Partial dissolution of silicate and glass fractions was assumed to significantly influence the release of Ca, Mg, Fe, K, Al and Si as well as Cu, Co and Zn. The formation of illite was suggested by the ORCHESTRA modelling to be one of the main solubility-controlling phases for major elements, whereas Co and Zn were controlled by CoO and zincite, respectively. Sorption of metals on hydrous ferric oxides was assumed to be an important attenuation mechanism, especially for the release of Pb and Cu. However, there is a high risk of Co, Cu, Pb and Zn mobility in the acidic soils around the smelter facility. Therefore, potential local options for “stabilisation” of the fly ash were evaluated on the basis of the modelling results using the PHREEQC code.     

Speciation and solubility relationships of Al, Cu and Fe in solutions associated with sulfuric acid leached mine waste rock

 Solutions from oxidized waste rock originating from an acid-leached waste dump were studied. The dissolution data suggest that after the majority of the soluble solid phases are removed, remaining solid phases continued to buffer the solutions in the acidic pH range. Incorporating the solution data into MINTEQA2 identified controls on the solubility of Al, Cu and Fe at pH values from about 2.5 to slightly over 5. Sulfate appears to play a significant role in the formation of solubility controlling solid phases for Al and Cu. This is not the case for Fe, and is suggested that Fe and Cu solubility may be controlled by cupric ferrite at low pH values. Received: 5 April 1998 · Accepted: 27 July 1998     

Metal partitioning in sediments and mineralogical controls on the acid mine drainage in Ribeira da Água Forte (Aljustrel,Iberian Pyrite Belt,Southern Portugal)

This work focuses on the geochemical processes taking place in the acid drainage in the Ribeira da Água Forte, located in the Aljustrel mining area in the Iberian Pyrite Belt. The approach involved water and stream sediment geochemical analyses, as well as other techniques such as sequential extraction, Mössbauer spectroscopy, and X-ray diffraction. Ribeira da Água Forte is a stream that drains the area of the old mine dumps of the Aljustrel mine, which have for decades been a source of acid waters. This stream flows to the north for a little over than 10 km, but mixes with a reduced, organic-rich, high pH waste water from the municipal waste water pools of the village. This water input produces two different results in the chemistry of the stream depending upon the season: (i) in the winter season, effective water mixing takes place, and the flux of acid water from the mine dumps is continuous, resulting in the immediate precipitation of the Fe from the acid waters; (ii) during the summer season, acid drainage is interrupted and only the waste water feeds the stream, resulting in the reductive dissolution of Fe hydroxides and hydroxysulfates in the stream sediments, releasing significant quantities of metals into solution. Throughout the year, water pH stays invariably within 4.0–4.5 for several meters downstream of this mixing zone even when the source waters come from the waste water pools, which have a pH around 8.4. The coupled interplay of dissolution and precipitation of the secondary minerals (hydroxides and sulfates), keeps the system pH between 3.9 and 4.5 all along the stream. In particular, evidence suggests that schwertmannite may be precipitating and later decomposing into Fe hydroxides to sustain the stream water pH at those levels. While Fe content decreases by 50% from solution, the most important trace metals are only slightly attenuated before the solution mixes with the Ribeira do Rôxo stream waters. Concentrations of As are the only ones effectively reduced along the flow path. Partitioning of Cu, Zn and Pb in the contaminated sediments also showed different behavior. Specific/non-specific adsorption is relevant for Cu and Zn in the upstream branch of Ribeira da Água Forte with acid drainage conditions, whereas the mixture with the waste water causes that the association of these metals with oxyhydroxide to be more important. Metals bound to oxyhydroxides are on the order of 60–70% for Pb, 50% for Cu and 30–60% for Zn. Organic matter is only marginally important around the waste water input area showing 2–8% Cu bound to this phase. These results also show that, although the mixing process of both acid and organic-rich waters can suppress and briefly mitigate some adverse effects of acid drainage, the continuing discharge of these waste waters into a dry stream promotes the remobilization of metals fixed in the secondary solid phases in the stream bed back into solution, a situation that can hardly be amended back to its original state.     

Geochemical evolution of highly alkaline and saline tank waste plumes during seepage through vadose zone sediments

Leakage of highly saline and alkaline radioactive waste from storage tanks into underlying sediments is a serious environmental problem at the Hanford Site in Washington State. This study focuses on geochemical evolution of tank waste plumes resulting from interactions between the waste solution and sediment. A synthetic tank waste solution was infused into unsaturated Hanford sediment columns (0.2, 0.6, and 2 m) maintained at 70°C to simulate the field contamination process. Spatially and temporally resolved geochemical profiles of the waste plume were obtained. Thorough OH⁻ neutralization (from an initial pH 14 down to 6.3) was observed. Three broad zones of pore solutions were identified to categorize the dominant geochemical reactions: the silicate dissolution zone (pH > 10), pH-neutralized zone (pH 10 to 6.5), and displaced native sediment pore water (pH 6.5 to 8). Elevated concentrations of Si, Fe, and K in plume fluids and their depleted concentrations in plume sediments reflected dissolution of primary minerals within the silicate dissolution zone. The very high Na concentrations in the waste solution resulted in rapid and complete cation exchange, reflected in high concentrations of Ca and Mg at the plume front. The plume-sediment profiles also showed deposition of hydrated solids and carbonates. Fair correspondence was obtained between these results and analyses of field borehole samples from a waste plume at the Hanford Site. Results of this study provide a well-defined framework for understanding waste plumes in the more complex field setting and for understanding geochemical factors controlling transport of contaminant species carried in waste solutions that leaked from single-shell storage tanks in the past.     

Release of toxic elements from rocks and mine wastes at the Furtei gold mine (Sardinia, Italy)

The Furtei gold mine in Sardinia (Italy) exploits a volcanic-hosted high-sulphidation epithermal deposit. Large amounts of materials derived from exploitation are present in open pits, waste rock dumps and cyanidation tailings impoundment. Mineralized rocks in outcrops and waste dumps contain significant amounts of sulphides (mainly pyrite and enargite). These materials have a high potential for acid drainage generation and release of toxic elements (notably Cu and As, but also Al, Ni, Co and Cd) as pointed out by laboratory leaching tests and in agreement with chemical composition of waters draining the mining area, that show pH as low as 2, up to 180 mg/L Cu, up to 5 mg/L As, and up to 788 mg/L Al. On the other hand, leaching solutions and waters interacting with mineral assemblages of the propylitic alteration zone (mainly composed of chlorite, quartz, and calcite, with relic magmatic plagioclase) show higher pH, and lower metal loads. Leachates from cyanidation tailings show variable pH (between 6.2 and 9.7, depending on sulphide content in tailings); cyanide concentration varies between 110 µg/L and about 3 mg/L, whereas contents of toxic elements in leachates are, with the exception of Hg, within the limits of Italian regulations for non-dangerous industrial wastes. Reclamation plans provide for confinement of tailings within specific repositories. This measure should effectively reduce the environmental impact of these materials. Reclamation plans should also include an adequate management of other high-sulphide wastes.     

Preoperational assessment of solute release from waste rock at proposed mining operations

Environmental assessments are conducted prior to mineral development at proposed mining operations. Among the objectives of these assessments is prediction of solute release from mine wastes projected to be generated by the proposed mining and associated operations. This paper provides guidance to those engaged in these assessments and, in more detail, provides insights on solid-phase characterization and application of kinetic test results for predicting solute release from waste rock. The logic guiding the process is consistent with general model construction practices and recent publications. Baseline conditions at the proposed site are determined and a detailed operational plan is developed and imposed upon the site. Block modeling of the mine geology is conducted to identify the mineral assemblages present, their masses and compositional variations. This information is used to select samples, representative of waste rock to be generated, that will be analyzed and tested to describe characteristics influencing waste rock drainage quality. The characterization results are used to select samples for laboratory dissolution testing (kinetic tests). These tests provide empirical data on dissolution of the various mineral assemblages present as waste rock. The data generated are used, in conjunction with environmental conditions, the proposed method of mine waste storage, and scientific and technical principles, to estimate solute release rates for the operational scale waste rock.Common concerns regarding waste rock are generation of acidic drainage and release of heavy metals and sulfate. Key solid phases in the assessments are those that dissolve to release acid and sulfate (iron sulfides, soluble iron sulfates, hydrated iron-sulfate minerals, minerals of the alunite–jarosite group), those that dissolve to neutralize acid (calcium and magnesium carbonates, silicate minerals), and those that release trace metals (trace metal sulfides, hydrated trace metal-sulfate minerals). Conventional mineralogic, petrographic, and geochemical analyses generally can be used to determine the quantities of these minerals present and to describe characteristics that influence their dissolution. A key solid-phase characteristic is the mineral surface area exposed for reaction, which is influenced by mode of occurrence (included, interstitial, liberated) and the extent of mineral surface coating. Short-term dissolution tests can estimate the extent of hydrated sulfate minerals present. Longer term dissolution tests are necessary to describe the dependence of drainage pH and solute release rates on solid-phase variation. The extensive data compiled from baseline pre-development definition, the operational plan, solid-phase characterization, and dissolution testing are ultimately synthesized by means of a modeling exercise requiring considerable technical and scientific expertise. The predicted rates (model outputs) are expressed as probability distributions to allow assessment of risk. This exercise must be technically defensible and transparent so that regulators can confidently assess the results and evaluate the operational plan proposed. Technical and non-technical challenges involved in implementing such programs are identified to benefit management planning for both industry and government.     

Geochemistry of iron ochres and mine waters from Levant Mine,Cornwall

The geochemistry of metal-rich mine waters and mineral precipitates from the Levant mine, Cornwall, has been examined. Sulphide oxidation at Levant mine has produced a wide range of secondary sulphides, oxides, chlorides, sulphates and carbonates in a gossan environment. The mine waters display a wide variation in alkalinity, pH, chloride, sulphate, sodium, potassium and heavy metal content which can be explained by variable degrees of mixing between acidic, metal-rich, rock drainage waters and neutral to alkaline sea waters. Transition metals are soluble in the acidic mine waters with concentrations up to 665 mg/l Cu, 41 mg/l Zn, 76 mg/l Mn, 6 mg/l Co and >2500 mg/l total Fe. The production of acid rock drainage and leaching of metals can be related to sulphide oxidation. Where these metal-rich acidic waters mix with infiltrated sea water, neutralization occurs and some metals are precipitated (principally Cu). Where pools of mine drainage are stagnant native copper and cuprite are precipitated, frequently observed replacing iron pipes and rail tracks and wooden shaft supports, due to electrode potential differences. In these solutions, dissolved copper species are also reduced by interaction with wood-derived organic species. Precipitation of iron oxyhydroxides, caused by a pH increase, also occurs and leads. to coprecipitation of other metals, including Cd, Co, Ph, Mn, Ag and Zn, thus limiting the release of dissolved metals in solution from the mine. However, the release of suspended metal-rich ochres in mine discharge waters (with high Ph, Zn, Cd, Mn, Ni, Sn, Sb, As, Bi, Cu, Co and Ag) will still present a potential environmental hazard.     

The role of disseminated calcite in the chemical weathering of granitoid rocks

Accessory calcite, present at concentrations between 300 and 3000 mg kg⁻¹, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO₂, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57–98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering.The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.     

Geochemical response of acid groundwater to neutralization by alkaline recharge

Solute transport and chemical neutralization (pH 3 to 7) within a shallow heterogeneous aquifer producing acid mine drainage (AMD) are examined at an abandoned surface coal mine in West Virginia. The aquifer is undergoing partial neutralization by mixing with alkalinity from a leaking sludge disposal pond, extending in preferential zones controlled by aquifer heterogeneity. Hydraulic heads interpolated from wells indicate leakage from a central alkaline (pH 7.1, 0.72 meq/L alkalinity) sludge pond is a principal source of recharge. Chemically-conservative sodium, added to AMD during treatment and leaked into the aquifer with the sludge, develops a dispersion plume over a restricted portion of the aquifer that correlates with pH, hydraulic head, and dissolved metals distributions. Concentrations of aluminum, iron, sulfate and acidity display higher concentrations downgradient from the pond as sludge alkalinity is consumed along flow paths. Before reaching springs, most dissolved iron is oxidized and hydrolyzed, likely precipitating in the aquifer as a ferric hydroxide or hydroxysulfate phase. The spatial pattern of iron and aluminum concentrations suggests accelerated oxidation caused by gas transport along the outer slopes of the spoil. Dissolved aluminum concentrations increase with total acidity, suggesting that dissolution of silicate minerals results from acidity released by iron hydrolysis. Neutralization reactions and higher pH are favored in more highly permeable portions of the spoil, where ferrihydrite and aluminum hydroxysulfate minerals (such as basaluminite) are supersaturated. In acid-producing zones at pH < 4.5, jurbanite is near equilibrium and an aluminum-sulfate phase with similar properties may limit aluminum concentrations, but become undersaturated in zones of advancing neutralization. At this particular site, ferrous iron produced by pyrite oxidation is almost completely oxidized over short transport distances, allowing hydrolysis of iron and aluminum should sufficient alkalinity be added to these acid waters.     

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.     

Geochemical response of acid groundwater to neutralization by alkaline recharge

Solute transport and chemical neutralization (pH 3 to 7) within a shallow heterogeneous aquifer producing acid mine drainage (AMD) are examined at an abandoned surface coal mine in West Virginia. The aquifer is undergoing partial neutralization by mixing with alkalinity from a leaking sludge disposal pond, extending in preferential zones controlled by aquifer heterogeneity. Hydraulic heads interpolated from wells indicate leakage from a central alkaline (pH 7.1, 0.72 meq/L alkalinity) sludge pond is a principal source of recharge. Chemically-conservative sodium, added to AMD during treatment and leaked into the aquifer with the sludge, develops a dispersion plume over a restricted portion of the aquifer that correlates with pH, hydraulic head, and dissolved metals distributions. Concentrations of aluminum, iron, sulfate and acidity display higher concentrations downgradient from the pond as sludge alkalinity is consumed along flow paths. Before reaching springs, most dissolved iron is oxidized and hydrolyzed, likely precipitating in the aquifer as a ferric hydroxide or hydroxysulfate phase. The spatial pattern of iron and aluminum concentrations suggests accelerated oxidation caused by gas transport along the outer slopes of the spoil. Dissolved aluminum concentrations increase with total acidity, suggesting that dissolution of silicate minerals results from acidity released by iron hydrolysis. Neutralization reactions and higher pH are favored in more highly permeable portions of the spoil, where ferrihydrite and aluminum hydroxysulfate minerals (such as basaluminite) are supersaturated. In acid-producing zones at pH < 4.5, jurbanite is near equilibrium and an aluminum-sulfate phase with similar properties may limit aluminum concentrations, but become undersaturated in zones of advancing neutralization. At this particular site, ferrous iron produced by pyrite oxidation is almost completely oxidized over short transport distances, allowing hydrolysis of iron and aluminum should sufficient alkalinity be added to these acid waters.     

The waste sulfuric acid lake of the TiO2-plant at Armyansk,Crimea, Ukraine. Part II. Modelling the chemical evolution with PHRQPITZ

The past and future evolution of a salt lake near Armyansk (Crimea, Ukraine), in which waste sulfuric acid has been discharged since 1969, is modelled using the equilibrium aqueous chemistry model PHRQPITZ. The initial lake is represented by a simplified salt solution, about 1.4 times concentrated average seawater. Since the waste acid contains iron and other metals, the effluent is modelled by an FeSO₄ solution of pH 1.04, containing minor amounts of Na and Mg. The PHRQPITZ model is adapted to describe precipitation of the trivalent Fe minerals natrojarosite and ferrihydrite. The yearly input of effluent constituents is assumed constant, and the input of water from the effluent is compensated by the yearly excess of evaporation over rainfall.According to the model, calcite dissolution from the underlying calcareous clays nearly buffers the increase in acidity of the lake by the effluent, maintaining pH at a value around 1.7, up to 16 a of operation (1986). Increase of Fe, Na, and SO₄ is buffered by precipitation of natrojarosite and gypsum. At the direct contact with the sediments a relatively impervious Fe (hydr)oxide layer develops. This hampers further reaction with the sediments, which effectively stops around 1992, when pH has reached a value of 0.85.It is predicted that with further increase in concentration, either through continued acid input or by evaporation of the acid lake, dissolution of previously precipitated natrojarosite first acts as a relative H buffer, followed by resumed precipitation of natrojarosite when the potential H increase is counterbalanced by the SO_4/HSO₄ association equilibrium. The concept of buffering in its strict sense does not apply, as conditional equilibrium constants for the extremely acid and concentrated conditions in the lake are far from constant and may differ significantly from their theoretical value.     

基于室内试验的四川峨眉—汉源高速廖山隧道碳酸盐岩溶蚀特征分析

廖山隧道是峨汉高速的控制性工程之一,隧址区岩溶地质条件复杂,为了深入研究隧址区碳酸盐岩的溶蚀特征,文章以隧址区中生界三叠系中统雷口坡组典型白云质灰岩、灰岩及钙质泥岩试样为研究对象,开展静态溶蚀试验,定量分析了碳酸盐岩溶蚀速率特征及相关影响因素,最后定性探讨了扫描电镜下试样溶蚀过程的微观结构变化。结果表明:（1）试验条件下（20 ℃、1 atm、乙酸溶液、pH=5.30、静态溶蚀）,隧址区雷口坡组灰岩溶蚀速率约3.48 mm/a,白云质灰岩溶蚀速率约1.57 mm/a,钙质泥岩溶蚀速率约0.90 mm/a;（2）碳酸盐岩的溶蚀受矿物组分及溶蚀环境控制,相同溶蚀环境下,溶蚀速率与方解石含量呈正相关,与白云石含量及溶蚀介质PH值呈负相关,总体上具有灰岩>白云质灰岩>钙质泥岩的特征;（3）有机酸与无机酸环境下灰岩溶蚀速率差异不大,总体趋势相同,而中性盐溶液与碱性环境则对灰岩溶蚀起到不同程度的抑制作用;（4）碳酸盐岩具有优先沿矿物成分、岩石微结构选择性溶蚀的特征,主要矿物含量的不同也使得碳酸盐岩的微观溶蚀过程存在一定差异。