Evaluating dual-domain models for upscaling multicomponent reactive transport in mine waste rock.

Reactive transport models have proven abilities to simulate the quantity and quality of drainage from mine waste rock. Tracer experiments indicate the presence of fast and slow flow regimes in many heterogeneous waste-rock piles. Although multidomain models have been developed specifically for systems with such distinctive hydrodynamics, there have been limited applications of multidomain reactive transport models to simulate composite drainage chemistries from waste-rock piles to date. This work evaluated the ability of dual-domain multicomponent reactive transport models (DDMRTMs) to reproduce breakthrough curves of conservative (chloride) and reactive (molybdenum) solutes observed at a well-characterized experimental waste-rock pile at the Antamina Mine, Peru. We found that the DDMRTM simulations quantitatively matched eight-year-long records of conservative transport through the waste-rock pile when parameterized mainly with field-measured properties obtained from the site and limited calibration. The DDMRTM model also provided a reasonable match to field observations of the reactive solute. The limited calibrated parameters are physically realistic, corroborating the ability of these multidomain models to reproduce the complex reactive-transport processes governing polluted rock drainage from large-scale waste-rock piles.

Reactive transport modelling to investigate multi-scale waste rock weathering processes.

Prediction of drainage quantity and quality is critical to reduce the environmental risks associated with weathering mine waste rock. Reactive transport models can be effective tools to understand and disentangle the processes underlying waste-rock weathering and drainage, but their validity and applicability can be impaired by poor parametrization and the non-uniqueness conundrum. Here, a process-based multicomponent reactive transport model is presented to interpret and quantify the processes affecting drainage quantity and quality from 15 waste- rock experiments from the Antamina mine, Peru. The deployed uniform flow formulation and consistent set of geochemical rate equations could be calibrated almost exclusively with measured bulk waste-rock properties in experiments ranging from 2 kg to 6500 tons in size. The quantitative agreement between simulated dynamics and the observed drainage records, for systems with a variety of rock lithologies and over a wide range of pH, supports the proposed selection of processes. The controls of important physicochemical processes and feedbacks such as secondary mineral precipitation, surface passivation, oxygen limitations, were confirmed through sensitivity analyses. Our work shows that reactive transport models with a consistent formulation and evidence-based parametrization can be used to explain waste-rock drainage dynamics across laboratory to field scales.

Evaluation of single- and dual-porosity models for reproducing the release of external and internal tracers from heterogeneous waste-rock piles.

Accurate predictions of solute release from waste-rock piles (WRPs) are paramount for decision making in mining-related environmental processes. Tracers provide information that can be used to estimate effective transport parameters and understand mechanisms controlling the hydraulic and geochemical behavior of WRPs. It is shown that internal tracers (i.e. initially present) together with external (i.e. applied) tracers provide complementary and quantitative information to identify transport mechanisms. The analysis focuses on two experimental WRPs, Piles 4 and Pile 5 at the Antamina Mine site (Peru), where both an internal chloride tracer and externally applied bromide tracer were monitored in discharge over three years. The results suggest that external tracers provide insight into transport associated with relatively fast flow regions that are activated during higher-rate recharge events. In contrast, internal tracers provide insight into mechanisms controlling solutes release from lower-permeability zones within the piles. Rate-limited diffusive processes, which can be mimicked by nonlocal mass-transfer models, affect both internal and external tracers. The sensitivity of the mass-transfer parameters to heterogeneity is higher for external tracers than for internal tracers, as indicated by the different mean residence times characterizing the flow paths associated with each tracer. The joint use of internal and external tracers provides a more comprehensive understanding of the transport mechanisms in WRPs. In particular, the tracer tests support the notion that a multi-porosity conceptualization of WRPs is more adequate for capturing key mechanisms than a dual-porosity conceptualization.

Molybdenum and zinc stable isotope variation in mining waste rock drainage and waste rock at the Antamina mine, Peru.

The stable isotope composition of molybdenum (Mo) and zinc (Zn) in mine wastes at the Antamina Copper-Zn-Mo mine, Peru, was characterized to investigate whether isotopic variation of these elements indicated metal attenuation processes in mine drainage. Waste rock and ore minerals were analyzed to identify the isotopic composition of Mo and Zn sources, namely molybdenites (MoS2) and sphalerites (ZnS). Molybdenum and Zn stable isotope ratios are reported relative to the NIST-SRM-3134 and PCIGR-1 Zn standards, respectively. δ(98)Mo among molybdenites ranged from -0.6 to +0.6‰ (n=9) while sphalerites showed no δ(66)Zn variations (0.11±0.01‰, 2 SD, n=5). Mine drainage samples from field waste rock weathering experiments were also analyzed to examine the extent of isotopic variability in the dissolved phase. Variations spanned 2.2‰ in δ(98)Mo (-0.1 to +2.1‰) and 0.7‰ in δ(66)Zn (-0.4 to +0.3‰) in mine drainage over a wide pH range (pH2.2-8.6). Lighter δ(66)Zn signatures were observed in alkaline pH conditions, which was consistent with Zn adsorption and/or hydrozincite (Zn5(OH)6(CO3)2) formation. However, in acidic mine drainage Zn isotopic compositions reflected the value of sphalerites. In addition, molybdenum isotope compositions in mine drainage were shifted towards heavier values (0.89±1.25‰, 2 SD, n=16), with some overlap, in comparison to molybdenites and waste rock (0.13±0.82‰, 2 SD, n=9). The cause of heavy Mo isotopic signatures in mine drainage was more difficult to resolve due to isotopic heterogeneity among ore minerals and a variety of possible overlapping processes including dissolution, adsorption and secondary mineral precipitation. This study shows that variation in metal isotope ratios are promising indicators of metal attenuation. Future characterization of isotopic fractionation associated to key environmental reactions will improve the power of Mo and Zn isotope ratios to track the fate of these elements in mine drainage.

A solubility and thermodynamic study of struvite.

Accumulation of magnesium ammonium phosphate hexahydrate (struvite) on surfaces in contact with wastewater, especially in anaerobic sludge digestion and post-digestion processes, is a widely reported problem in the wastewater treatment industry. The solubility and thermodynamic properties of struvite at different temperatures was studied. Struvite thermodynamic solubility products at temperatures between 10 and 60 'C were determined by variation of solution ionic strength and extrapolation to zero ionic strength, using an appropriate activity coefficient model. The pKsp value of struvite at 25 degrees C was found to be 13.36 (+/-0.07). The pKsp value for a temperature range of 10-60 degrees C varies from 14.36 (+/-0.05) to 14.01 (+/-0.03) with the minimum value of 13.17 (+/-0.05) at 30 degrees C. The effect of ionic strength, pH and temperature on struvite solubility was also studied. The solubility of struvite determined in deionized water was found to be 169.2 (+/-4.3) mg l(-1) at 25 degrees C, with the maximum value of 212.7 (+/-3.8) mg l(-1) at 35 degrees C. Standard enthalpy of reaction, delta Hr degrees calculated from the average Ksp values for the temperature range of 10-30 degrees C, was 23.62 Kcal mol(-1). An analytical expression for the Ksp as a function of temperature has been developed by fitting experimental data.