Multiphase transfer processes in waste rock piles producing acid mine drainage: 2. Applications of numerical simulation

Acid mine drainage (AMD) results from the oxidation of sulfides, mainly pyrite, present in mine wastes, either mill tailings or waste rock. This is the second of two papers describing the coupled physical processes taking place in waste rock piles undergoing AMD production. Since the oxidation of pyrite involves the consumption of oxygen and the production of heat, the oxidation process initiates coupled processes of gas transfer by diffusion and convection as well as heat transfer. These processes influence the supply of oxygen that is required to sustain the oxidation process. This second paper describes a numerical simulator used to represent the interaction of these coupled transfer processes. Numerical simulations are applied to two large sites with extensive characterization programs and widely different properties and behavior that were described in the first paper. The South Dump of the Doyon mine in Canada is permeable and has a high pyrite oxidation rate, thus making temperature-driven air convection the main oxygen supply mechanism. The Nordhalde of the Ronnenberg mining district in Germany contains lower permeability material which is less reactive, thus leading to a more balanced contribution of gaseous diffusion and convection as oxygen supply mechanisms. Overall, simulations allow a coherent representation of the conditions monitored within the waste rock piles and the confirmation of their physical properties. Conceptual simulations are also carried out to illustrate the potential effect of border membranes and layered co-mingling as mitigation methods used to control AMD production in either active or future waste rock piles.     

Multiphase transfer processes in waste rock piles producing acid mine drainage 1: Conceptual model and system characterization.

Acid mine drainage (AMD) results from the oxidation of sulfides, mainly pyrite, present in mine wastes, either mill tailings or waste rock. This is the first of two papers describing the coupled physical processes taking place in waste rock piles undergoing AMD production. Since the oxidation of pyrite involves the consumption of oxygen and the production of heat, the oxidation process initiates coupled processes of gas transfer by diffusion and convection as well as heat transfer. These processes influence the supply of oxygen that is required to sustain the oxidation process. This first paper describes a general conceptual model of the interaction of these coupled transfer processes. This general conceptual model is illustrated by the physicochemical conditions observed at two large sites where extensive characterization programs revealed widely different properties. The South Dump of the Doyon mine in Canada is permeable and has a high pyrite oxidation rate leading to high temperatures (over 65 degrees C), thus making temperature-driven air convection the main oxygen supply mechanism. The Nordhalde of the Ronnenberg mining district in Germany contains lower permeability material which is less reactive, thus leading to a more balanced contribution of gaseous diffusion and convection as oxygen supply mechanisms. The field characterization and monitoring data at these sites were thoroughly analyzed to yield two coherent sets of representative physical properties. These properties are used in the second paper as a basis for applications of numerical simulation in AMD-producing waste rock piles.     

Geochemical characterization of acid mine drainage from a waste rock pile, Mine Doyon, Québec, Canada

Water quality in the unsaturated and saturated zones of a waste rock pile containing sulphides was investigated. The main objectives of the project were (1) the evaluation of geochemical trends including the acid mine drainage (AMD)-buffering mechanism and the role of secondary minerals, and (2) the investigation of the use of stable isotopes for the interpretation of physical and geochemical processes in waste rock. Pore water in unsaturated zone was sampled from suction lysimeters and with piezometers in underlying saturated rocks. The investigation revealed strong temporal (dry period vs. recharge period), and spatial (slope vs. central region of pile) variability in the formation of acid mine drainage. The main secondary minerals observed were gypsum and jarosite. There was a higher concentration of gypsum in solid phase at Site TBT than at Site 6, suggesting that part of the gypsum formed at Site 6 in the early stage of AMD has been already dissolved. Formation of secondary minerals contributed to the formation of AMD by opening of foliation planes in waste rock, thus increasing the access of oxidants like O2 and Fe3+ to previously encapsulated pyrite. The behavior of several dissolved species such as Mg, Al, and Fe2+ can be considered as conservative in the leachate. Stable isotopes, deuterium and 18O, indicated internal evaporation within the pile, and were used to trace recharge pulses from snowmelt. Isotope trends for 34S and 18O(SO4) indicated a lack of sulfate reduction and zones of active oxidation of pyrite, respectively. Results of numerical modeling of pyrite oxidation and gas and water transport were consistent with geochemical and isotopic trends and confirmed zones of high evaporation rate within the rock pile close to the slope. The results indicate that physical and chemical processes within the pile are strongly coupled and cannot be considered separately when oxidation rates are high and influence gas transport as a result of heat generation.     

Use of O2 consumption and CO2 production in kinetic cells to delineate pyrite oxidation-carbonate buffering and microbial respiration in unsaturated media

Identifying zones of sulphide oxidation and carbonate buffering is important in the development of a management plan for mine waste-rock piles. In this study, we used a kinetic cell technique to measure rates of O2 consumption and CO2 production in low sulphide (<0.12 wt.% S), low inorganic carbon (<0.20 wt.% C(inorganic)), gneissic waste rock and associated organic-rich lake sediment (0.7 wt.% C(organic)), and forest soil (1.4 wt.% C(organic)) collected from the Key Lake uranium mine in Saskatchewan, Canada. Solid chemistry, stable carbon isotope, pore water sulphate concentration data, and stoichiometric considerations indicated that O2 consumption and CO2 production were constrained by microbial respiration in the lake sediment and forest soil and by pyrite oxidation-carbonate buffering in the gneissic waste rock. Mean ratios of molar CO2 production to O2 consumption rates were 0.5 for lake sediment, 0.7 for forest soil, and 0.2 for gneissic waste rock. The different O2/CO2 ratios suggested that O2-CO2 monitoring may provide a practical tool for identifying the zones of microbial respiration and pyrite oxidation-carbonate buffering in mine waste-rock piles. Rates of O2 consumption and CO2 production were about one order of magnitude greater in lake sediment than in gneissic waste rock, indicating that microbial respiration would exert a control on the distribution of O2 and CO2 gas in waste-rock piles constructed upon the dewatered lake sediments.     

粪便与生活垃圾混合堆肥过程控制

采用强制通风静态仓进行粪便和生活垃圾混合堆肥,以玉米秸为调理剂,石灰调节pH,考察正压鼓风和负压抽吸2种通风方式对不同堆料配比堆肥过程的控制效果。试验结果表明,5种堆料配比的中层温度都达到了50℃,并保持了5 d以上,达到了堆肥无害化和稳定化的要求。正压鼓风堆料底部温度较低,负压抽吸堆料底部热量容易聚集,但是后者堆体温度分布相对均匀。负压抽吸对水分的去除效果差于正压鼓风。对于温度未达到50℃的堆料应回流处理保证无害化。粪便有机物含量高,堆肥初期易酸化,添加石灰调节pH,使堆肥顺利升温,缩短发酵期,石灰合理添加量为2%(质量分数)。采用负压抽吸的通风方式,散除堆肥初期的挥发性有机酸,再经过冷凝除臭器脱酸除臭后排放,是一种可取的方式。     

Analytical model of solute transport by unsteady unsaturated gravitational infiltration

Penetration of reactive solute into a soil during a cycle of water infiltration and redistribution is investigated by deriving analytical closed form solutions for fluid flux, moisture content and contaminant concentration. The solution is developed for gravitational flow and advective transport and is applied to two scenarios of solute applications encountered in the applications: a finite pulse of solute dissolved in irrigation water and an instantaneous pulse broadcasted onto the soil surface. Through comparison to simulations of Richards' flow, capillary suction is shown to have contrasting effects on the upper and lower boundaries of the fluid pulse, speeding penetration of the wetting front and reducing the rate of drying. This leads to agreement between the analytical and numerical solutions for typical field and experimental conditions. The analytical solution is further incorporated into a stochastic column model of flow and transport to compute mean solute concentration in a heterogeneous field. An unusual phenomenon of plume contraction is observed at long times of solute propagation during the drying stage. The mean concentration profiles match those of the Monte-Carlo simulations for capillary length scales typical of sandy soils.     

Effect of aggregate storage piles configuration on dust emissions

Fugitive dust emissions from stockpiles in the open storage yards of industrial sites and the subsequent atmospheric dust dispersion have brought about many ecological and economical problems. This paper introduces a new approach to estimate emission rates using data from Computational Fluid Dynamics simulations. Flow around stockpiles of varying configurations was studied using a previously validated numerical model. Different pile height scenarios, corresponding to a constant material volume and a fixed angle of repose, were exposed to various wind speeds. Flow analysis over the piles showed the importance of using 3D simulations to fully understand the close linkage between flow processes and particles uptake. Data obtained were then integrated in order to evaluate dust emission rates. Results provide evidence to suggest that changing pile configuration can reduce dust emissions. It was found that, for the range of wind conditions and pile dimensions tested, the intermediate pile height configurations lead to a better overall protecting effect from wind and thus were found to produce lower dust emissions.     

Fate of nitrogen for subsurface drip dispersal of effluent from small wastewater systems

Subsurface drip irrigation systems apply effluent from onsite wastewater systems in a more uniform manner at a lower rate than has been possible with other effluent dispersal methods. The effluent is dispersed in a biologically active part of the soil profile for optimal treatment and where the water and nutrients can be utilized by landscape plants. Container tests were performed to determine the fate of water and nitrogen compounds applied to packed loamy sand, sandy loam, and silt loam soils. Nitrogen removal rates measured in the container tests ranged from 63 to 95% despite relatively low levels of available carbon. A Hydrus 2D vadose zone model with nitrification and denitrification rate coefficients calculated as a function of soil moisture content fit the container test results reasonably well. Model results were sensitive to the denitrification rate moisture content function. Two-phase transport parameters were needed to model the preferential flow conditions in the finer soils. Applying the model to generic soil types, the greatest nitrogen losses (30 to 70%) were predicted for medium to fine texture soils and soils with restrictive layers or capillary breaks. The slow transport with subsurface drip irrigation enhanced total nitrogen losses and plant nitrogen uptake opportunity.     

制浆废液降低普钙水分的应用研究

针对我国采用高临界流动水分的磷矿进行湿法生产普钙普遍存在产品水分达不到部颁标准的难题,直接采用制浆废液(利用其主要对环境有害成分之一--MNA作减水剂)进行降低普钙水分的研究和应用.实验结果表明,添加少量的减水剂MNA可显著降低国内朝阳、昆阳、浏阳和国外摩洛哥等单种磷矿以及昆阳-朝阳混矿的矿浆粘度和水分.采用国产昆阳-朝阳混矿进行工业生产试验结果表明,添加0.35%～0.4%干矿粉重量的减水剂MNA,不仅可使球磨添加水量从145 kg降至103 kg,矿浆含水量从30.5%降至27%,成品肥含水量从16.24%降至13.77%,而且可使有效磷从10.67%升至12.24%,转化率由86.57%提高到90.45%,矿浆细度由90.18%提高到93.12%.实验和工业生产试验表明,直接用造纸制浆废液降低普钙水分,既确保和改善了普钙的产品质量,又治理了环境污染,取得了较好的经济、环境和社会效益.     

垃圾填埋场甲烷氧化菌及甲烷通量的研究

采用静态箱法、滚管计数法和气相色谱法,对6个不同封场时间填埋区的甲烷通量、覆土层甲烷氧化菌数量和甲烷氧化速率的变化趋势进行了测定,并分析了它们与封场时间、植被覆盖率等因素之间的相关性。结果发现6个填埋区甲烷通量的变化范围在-0.34～5.31 mg/(m2.h)之间;覆土层甲烷氧化菌的数量范围为3.10×107～20.77×107 cfu/g干土,甲烷氧化速率在1.65×10-8～4.34×10-8mol/(h.g)之间。覆土层甲烷氧化菌的数量与甲烷氧化速率呈正相关,但前者并不是后者的决定性因素;甲烷通量高时可刺激甲烷氧化菌数量及氧化速率的提高,且三者均与封场时间呈显著负相关,与植被覆盖率呈负相关;当含水率大于15%时,随着覆土层含水率的增加,甲烷氧化速率呈下降趋势;覆土pH、有机质和铵态氮与甲烷氧化速率等无明显相关性。提高覆土层的甲烷氧化速率可有效减少垃圾填埋场的甲烷排放。     

Modelling of physical and reactive processes during biodegradation of a hydrocarbon plume under transient groundwater flow conditions

Numerical experiments of non-reactive and reactive transport were carried out to quantify the influence of a seasonally varying, transient flow field on transport and natural attenuation at a hydrocarbon-contaminated field site. Different numerical schemes for solving advective transport were compared to assess their capability to model low transversal dispersivities in transient flow fields. For the field site, it is shown that vertical plume spreading is largely inhibited, particularly if sorption is taken into account. For the reactive simulations, a biodegradation reaction module for the geochemical transport model PHT3D was developed. Results of the reactive transport simulations show that under the site-specific conditions the temporal variations in groundwater flow do, to a modest extent, affect average biodegradation rates and average total (dissolved) contaminant mass in the aquifer. The model simulations demonstrate that the seasonal variability in groundwater flow only results in significantly enhanced biodegradation rates when a differential sorption of electron donor (toluene) and electron acceptor (sulfate) is assumed.     

Field-scale operation of methane biofiltration systems to mitigate point source methane emissions

Methane biofiltration (MBF) is a novel low-cost technique for reducing low volume point source emissions of methane (CH₄). MBF uses a granular medium, such as soil or compost, to support the growth of methanotrophic bacteria responsible for converting CH₄ to carbon dioxide (CO₂) and water (H₂O). A field research program was undertaken to evaluate the potential to treat low volume point source engineered CH₄ emissions using an MBF at a natural gas monitoring station. A new comprehensive three-dimensional numerical model was developed incorporating advection-diffusive flow of gas, biological reactions and heat and moisture flow. The one-dimensional version of this model was used as a guiding tool for designing and operating the MBF. The long-term monitoring results of the field MBF are also presented. The field MBF operated with no control of precipitation, evaporation, and temperature, provided more than 80% of CH₄ oxidation throughout spring, summer, and fall seasons. The numerical model was able to predict the CH₄ oxidation behavior of the field MBF with high accuracy. The numerical model simulations are presented for estimating CH₄ oxidation efficiencies under various operating conditions, including different filter bed depths and CH₄ flux rates. The field observations as well as numerical model simulations indicated that the long-term performance of MBFs is strongly dependent on environmental factors, such as ambient temperature and precipitation.     

Infiltration and redistribution of perchloroethylene in partially saturated, stratified porous media

Contamination of the subsurface by nonaqueous phase liquids (NAPLs) is a widespread problem. To investigate the behavior of a nonspreading, dense NAPL (DNAPL) in the vadose zone, we conducted perchloroethylene (PCE) infiltration experiments in nominally 1- and 2-dimensional (D), stratified porous media. In addition, the usefulness and limitations of a multifluid flow simulator to describe PCE infiltration and redistribution under the experimental conditions were tested. The physical simulations were conducted in a column (1-D) and a flow container (2-D) which were packed with two distinct layers of coarse-grained sand and a fine-grained sand layer in between. Volumetric water and PCE contents were determined with a fully automated dual-energy gamma radiation system. While migrating through the drier parts of the coarse-grained sand layers, PCE appeared to wet the water–air interface rather than displacing any water. In the wetter parts of the porous medium, PCE displaced water and behaved as a true nonwetting fluid. PCE showed a limited response to gradients in capillary pressure and rather high values for the volumetric PCE content were measured in the fine-grained sand layers. This was attributed to the nonspreading nature of PCE. The multifluid flow simulator appeared to predict the initial PCE movement in the vadose zone reasonably well. However, the model was not capable of predicting the final amounts of PCE retained in either the unsaturated or saturated part of the flow domain, mainly because the simulator does not consider the nonspreading flow behavior of NAPLs.     

A composite medium approximation for unsaturated flow in layered sediments

Saturated-unsaturated flow in strictly layered sediments proceeds via conductors in parallel in the direction parallel to bedding, and via resistors in series in the direction perpendicular to bedding. On sufficiently small scales of space and time, flow in such media will be subject to approximate capillary equilibrium locally, which provides a basis for approximating the effective hydraulic conductivity of a composite multi-layer medium in terms of the conductivities of the individual layers. Equations for the hydraulic conductivity tensor in "composite medium approximation" (COMA) are given in a coordinate system aligned with bedding. Hydraulic conductivity parallel to bedding is generally larger than in the perpendicular direction. The anisotropy depends on the spread of the conductivity distribution, and tends to increase for dryer conditions. The COMA model was implemented in a multi-phase flow simulator and tested by comparison with high-resolution simulations in which all layering heterogeneity is resolved explicitly. Under favorable conditions, COMA is found to accurately represent sub-grid scale flow and transport processes, providing a practical method for simulating field-scale flow and transport in layered media. The approximation improves when layers are thinner, and when flow rates are smaller.     

Chemisorption of hydrogen sulphide and methanethiol by light expanded clay aggregates (Leca)

Removal of volatile sulphur compounds from livestock waste air by biological air filtration may be enhanced by application of packing materials with reactive properties. In this study, light expanded clay aggregates (Leca®) was tested with respect to sorption and potential chemical degradation of H₂S, Methanethiol (MT) and Dimethyl sulphide (DMS). Leca was selected due to its content of minerals, including iron, and due to its high specific surface area. The performance of Leca was evaluated based on breakthrough curves and by comparing the difference between the inlet and outlet gas concentrations. Whereas DMS did not appear to be removed by Leca, both H₂S and MT were removed with variable efficiency depending on the specific conditions. Dimethyl disulphide (DMDS) and dimethyl trisulphide (DMTS) were demonstrated to be produced during the degradation process in relatively high yields. A comparison between ambient air and nitrogen gas conditions showed that the chemisorption of H₂S and MT did not necessarily need oxygen to be present. X-ray analysis of Leca showed an abundance of Fe₂O₃. It is therefore hypothesized that Fe₂O₃ in Leca can remove H₂S and MT by chemisorption. Both air velocity and moisture content clearly affected the capacity of Leca for removal of H₂S and MT. Lower removal is seen at higher air velocities, whereas higher moisture content enhances removal. However, chemisorption of MT by Leca appears to be limited above a threshold moisture level. Potential reaction mechanisms are discussed in relation to the observed effects. The results implicate that Leca can be used as a filter material with reactive properties provided that moisture content is controlled and that an adequate air velocity is used.     

Prevention of sulfide oxidation in waste rock by the addition of lime kiln dust

During the operation of a mine, waste rock is often deposited in heaps and usually left under ambient conditions allowing sulfides to oxidize. To focus on waste rock management for preventing acid rock drainage (ARD) formation rather than ARD treatment could avoid its generation and reduce lime consumption, costs, and sludge treatment. Leachates from 10 L laboratory test cells containing sulfide-rich (>?60% pyrite) waste rock with and without the addition of lime kiln dust (LKD) (5 wt.%) were compared to each other to evaluate the LKD’s ability to maintain near neutral pH and reduce the sulfide oxidation. Leaching of solely waste rock generated an acidic leachate (pH?<?1.3) with high concentrations of As (21 mg/L), Cu (20 mg/L), Fe (18 g/L), Mn (45 mg/L), Pb (856 μg/L), Sb (967 μg/L), S (17 g/L), and Zn (23 mg/L). Conversely, the addition of 5 wt.% LKD generated and maintained a near neutral pH along with decreasing of metal and metalloid concentrations by more than 99.9%. Decreased concentrations were most pronounced for As, Cu, Pb, and Zn while S was relatively high (100 mg/L) but decreasing throughout the time of leaching. The results from sequential extraction combined with element release, geochemical calculations, and Raman analysis suggest that S concentrations decreased due to decreasing sulfide oxidation rate, which led to gypsum dissolution. The result from this study shows that a limited amount of LKD, corresponding to 4% of the net neutralizing potential of the waste rock, can prevent the acceleration of sulfide oxidation and subsequent release of sulfate, metals, and metalloids but the quantity and long-term stability of secondary minerals formed needs to be evaluated and understood before this method can be applied at a larger scale.

     

Neutralization/prevention of acid rock drainage using mixtures of alkaline by-products and sulfidic mine wastes

Backfilling of open pit with sulfidic waste rock followed by inundation is a common method for reducing sulfide oxidation after mine closure. This approach can be complemented by mixing the waste rock with alkaline materials from pulp and steel mills to increase the system’s neutralization potential. Leachates from 1 m³ tanks containing sulfide-rich (ca.30 wt %) waste rock formed under dry and water saturated conditions under laboratory conditions were characterized and compared to those formed from mixtures. The waste rock leachate produced an acidic leachate (pH?<?2) with high concentrations of As (65 mg/L), Cu (6 mg/L), and Zn (150 mg/L) after 258 days. The leachate from water-saturated waste rock had lower concentrations of As and Cu (<2 μg/L), Pb and Zn (20 μg/L and 5 mg/L), respectively, and its pH was around 6. Crushed (<6 mm) waste rock mixed with different fractions (1–5 wt %) of green liquid dregs, fly ash, mesa lime, and argon oxygen decarburization (AOD) slag was leached on a small scale for 65 day, and showed near-neutral pH values, except for mixtures of waste rock with AOD slag and fly ash (5 % w/w) which were more basic (pH?>?9). The decrease of elemental concentration in the leachate was most pronounced for Pb and Zn, while Al and S were relatively high. Overall, the results obtained were promising and suggest that alkaline by-products could be useful additives for minimizing ARD formation.     

A mountain-scale thermal-hydrologic model for simulating fluid flow and heat transfer in unsaturated fractured rock

A multidimensional, mountain-scale, thermal-hydrologic (TH) numerical model is presented for investigating unsaturated flow behavior in response to decay heat from the proposed radioactive waste repository in the Yucca Mountain unsaturated zone (UZ), The model, consisting of both two-dimensional (2-D) and three-dimensional (3-D) representations of the UZ repository system, is based on the current repository design, drift layout, thermal loading scenario, and estimated current and future climate conditions. This mountain-scale TH model evaluates the coupled TH processes related to mountain-scale UZ flow. It also simulates the impact of radioactive waste heat release on the natural hydrogeological system, including heat-driven processes occurring near and far away from the emplacement tunnels or drifts. The model simulates predict thermally perturbed liquid saturation, gas- and liquid-phase fluxes, and water and rock temperature elevations, as well as the changes in water flux driven by evaporation/condensation processes and drainage between drifts. These simulations provide insights into mountain-scale thermally perturbed flow fields under thermal loading conditions.     

Simulation of organic liquid flow in porous media using estimated and measured transport properties

Many numerical models which describe the movement of a separate organic liquid phase in the subsurface require information about the relationships between capillary pressure and saturation, and between relative permeability and saturation. An evaluation of the information available for these relationships suggests that substantial discrepancies may be introduced into simulations if estimated, rather than measured, data are employed. The purpose of this study was to quantify these deviations. Two-phase displacement simulations were performed in one and two dimensions for several organic liquid-water systems. Both constant-head and constant-flux boundary conditions were employed at a variety of flow rates and time scales, using both measurements and estimates of capillary pressure and relative permeability for a sandy aquifer material. The results demonstrate that the use of estimated transport relationships produces significantly different predictions of organic liquid migration. The magnitude of the deviations between predictions may be as high as 25% or more after relatively short displacement periods, depending on the boundary conditions of the simulated scenario, as well as on the physical characteristics of the two-phase system. For the systems examined, most of the deviations resulted from the estimates for relative permeability to the organic liquid. Thus, improved methods for the estimation of the relative permeability to the organic liquid are needed to reduce the uncertainty in displacement simulations.     

Numerical modeling of coupled variably saturated fluid flow and reactive transport with fast and slow chemical reactions

The couplings among chemical reaction rates, advective and diffusive transport in fractured media or soils, and changes in hydraulic properties due to precipitation and dissolution within fractures and in rock matrix are important for both nuclear waste disposal and remediation of contaminated sites. This paper describes the development and application of LEHGC2.0, a mechanistically based numerical model for simulation of coupled fluid flow and reactive chemical transport, including both fast and slow reactions in variably saturated media. Theoretical bases and numerical implementations are summarized, and two example problems are demonstrated. The first example deals with the effect of precipitation/dissolution on fluid flow and matrix diffusion in a two-dimensional fractured media. Because of the precipitation and decreased diffusion of solute from the fracture into the matrix, retardation in the fractured medium is not as large as the case wherein interactions between chemical reactions and transport are not considered. The second example focuses on a complicated but realistic advective-dispersive-reactive transport problem. This example exemplifies the need for innovative numerical algorithms to solve problems involving stiff geochemical reactions.