Recovery of rare earth elements from acidic mine waters: An unknown secondary resource.

Acidic mine Drainage (AMD) is still considered one of the greatest mining sustainability challenges due to the large volumes of wastes generated and the high associated treatment cost. New regulation initiatives on sustainable development, circular economy and the need for strategic elements as Rare Earth Elements (REE) may overcome the traditional research initiatives directed to developing low cost treatment options and to develop research initiatives to identify the potential benefit of considering such AMD as a potential secondary resource. As an example, this study develops the integration of a three-stage process where REE are selectively separated from base metals (e.g. Fe, Al, Mn, Ca, Mg, Cd, Pb) and then concentrate to produce a rich REE by-product recovered as REE-phosphates. Selective separation of Fe (>99%) was achieved by total oxidation to Fe(III) and subsequent precipitation as schwertmannite at pH 3,6 ± 0.2. REE were then extracted from AMD using a sulfonic ion-exchange resin to produce concentrated REE sulfuric solutions up to 0.25 gREE/L. In a final stage selective separation of REE from Al(III), Ca(II) and Mg(II) and transitions elements (Cu, Zn, Ni) was achieved by precipitation with phosphate solutions under optimized pH control and total phosphate concentration. XRD analysis identified low-crystalline minerals. By using a thermal treatment the presence of PrPO4(s) and Cheralite (CePO4(s)) where Ce is substituted by La and Ca and Xenotime (YPO4(s)) were found as main minerals AlPO4(s) Ca,MgYPO4(s) were also identified.

In situ removal of arsenic from groundwater by using permeable reactive barriers of organic matter/limestone/zero-valent iron mixtures.

In this study, two mixtures of municipal compost, limestone and, optionally, zero-valent iron were assessed in two column experiments on acid mine treatment. The effluent solution was systematically analysed throughout the experiment and precipitates from both columns were withdrawn for scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry analysis and, from the column containing zero-valent iron, solid digestion and sequential extraction analysis. The results showed that waters were cleaned of arsenic, metals and acidity, but chemical and morphological analysis suggested that metal removal was not due predominantly to biogenic sulphide generation but to pH increase, i.e. metal (oxy)hydroxide and carbonate precipitation. Retained arsenic and metal removal were clearly associated to co-precipitation with and/or sorption on iron and aluminum (oxy)hydroxides. An improvement on the arsenic removal efficiency was achieved when the filling mixture contained zero-valent iron. Values of arsenic concentrations were then always below 10 microg/L.

Towards more sustainable brine extraction in salt flats: Learning from the Salar de Atacama.

Salt flats are hydrogeological systems with highly valuable wetland and lake ecosystems. The brine pumping carried out to extract lithium is modifying the natural evaporation discharge of salt flats. A methodology to evaluate the impacts caused on water table and evaporation discharge by brine exploitation in salt flats is proposed and applied to the Salar de Atacama. The methodology included field measurements of water table and evaporation rate, followed by its spatio-temporal analysis and the application of the results to a numerical model to improve the brine exploitation design. The spatio-temporal analysis of the water table depth and evaporation rates measured in the field concluded that the evaporation discharge decreased from 12.85 to 10.95 m3·s-1 between 1986 and 2018, that is around 15%. This reduction compensated part of the extractions and could contribute to the preservation of the mixing zone ecosystems. At present, this damping capacity is already amortized in the nucleus and the marginal zone is beginning to be affected by the brine pumping. The sensitivity of the phreatic evaporation on the water table depth justified the great uncertainty of the previous evaporation discharge estimations. Thus, an average error lower than 0.5 m was enough to modify the evaporation by >60%. Therefore, considerable effort should invested to faithfully quantify the discharge by evaporation which is critical in water balance of salt flat basins. The numerical model pointed out that the total pumping outflow should be distributed in the largest possible area. This minimizes the water table drawdown and maximizes the capacity of the evaporation decline to compensate the extractions. The results of this work serve as guidelines to improve the efficiency of future salt flat exploitations.

Hydrogeological constraints for the genesis of the extreme lithium enrichment in the Salar de Atacama (NE Chile): A thermohaline flow modelling approach.

The Salar de Atacama (SdA) is the largest Li reserve globally. The origin of Li, together with the rest of solutes, has been object of debate. Thus, rock weathering at low temperature, hydrothermal leaching or magmatic origin together with subsequent evaporation has been hypothesized. However, the extreme Li enrichment (>4000 mg/L) and the location of the Li-Mg-rich brines around the Salar Fault System (SFS) that crosses the nucleus of the SdA in half remain unexplained. The objective of this work is to define the thermohaline groundwater flow in the SdA basin to account for the genesis of its extreme Li enrichment. Thermohaline flow modelling has demonstrated the critical effect of the minimum hydraulic head (MHH) of the regional water table on the groundwater flow of salt flats. The MHH divides the basin into two isolated hydrodynamic systems and constitutes the endpoint towards which the most evaporated brines converge. The spatial mismatch between the locations of the Li-Mg-rich brines in the central-western zone of the nucleus (in the SFS) and the MHH in the easternmost zone of the nucleus discards recent evaporative concentration of the recharge water as the main mechanism of Li enrichment. Moreover, the persistence of a saline interface surrounding the nucleus at depth, regardless of the temperature gradient, also precludes lateral recharge (predominantly from the east) to ascend along the SFS. On the other hand, the computed thermohaline flow is compatible with the remobilization of buried layers of Li-Mg-enriched salts and/or clays by dilute recharge waters coming from the west or southwest of the basin. Here, the role of faults and density-driven flow is key to allow efficient downward and upward flow rates that favour the remobilization of Li and Mg.

The effect of brine pumping on the natural hydrodynamics of the Salar de Atacama: The damping capacity of salt flats.

The Salar de Atacama is used as a case study to analyse and quantify coupled natural (evaporation and recharge) and anthropogenic processes (pumping of lithium-rich brine) to abstract their patterns to other salt flats using a three-dimensional groundwater flow model. Important changes in the dynamics of the water table between the pre-operational period (1986-1994) and operational period (1994-2015) are observed. The water table exhibited a gradual drawdown during the pre-operational period because the evaporation was greater than the recharge for most of these periods. This negative balance was counteracted by some sharp rises that were produced by direct rainfall events on the salt flat. The deep lateral recharge that arrived from the mountains did not produce abrupt changes in the water table because the rainfall events in the mountains were damped by the distance of the recharge zone and great thickness of the unsaturated zone. The natural evolution of the water table was modified by the intensive brine pumping that was performed in the south-western Salar de Atacama during the operational period. As evaporation depends on the water table depth, the pumping caused a drawdown of the water table, resulting in an evaporation rate reduction that partially compensated for the pumped brine in the water balance of the basin. This effect is defined as the damping capacity of salt flats. Thus, salt flats have a high capacity for dampening oscillations in their water table in response to both natural and anthropogenic disturbances which is of great importance for the management of lake and wetland ecosystems and brine exploitation. The limit of the dampening capacity of salt flats is defined by the evaporation extinction depth, which is in the range of 0.5-2 m.

Hydrodynamics of salt flat basins: The Salar de Atacama example.

The Salar de Atacama is one of the most well-known saline endorheic basins in the world. It accumulates the world main lithium reserves and contains very sensitive ecosystems. The objective of this work is to characterize the hydrodynamics of the Salar de Atacama, and to quantify its complex water balance prior to the intense brine extraction. The methodology and results can be extrapolated to the groundwater flow and recharge of other salt flats. A three-dimensional groundwater flow model using low computational effort was calibrated against hundreds of hydraulic head measurements. The water infiltrated from the mountains ascends as a vertical flux through the saline interface (mixing zone) produced by the density contrast between the recharged freshwater and the evaporated brine of the salt flat nucleus. This water discharges and is largely evaporated from lakes or directly from the shallow water table. On the other hand, the very low hydraulic gradients, coupled with the presence of the mixing zone that operates as barrier, leads the salt flat nucleus to act as a hydrodynamically quasi-isolated area. The computed water table shows the lowest hydraulic head in the salt flat nucleus near the discharge at the mixing zone. The groundwater balance of the Salar de Atacama in its natural regime was quantified resulting in an inflow/outflow of 14.9 m3·s-1. This balance considers the basin as an endorheic system. The very low infiltration values that are generally assumed for hyperarid basins are not consistent with the hydrogeology of the Salar de Atacama. Indeed, very high infiltration rates (up to 85% of rainfall) occur because of the high degree of fracturing of rocks and the scarce vegetation. This high infiltration is consistent with the light isotopic composition of the water from the recharge area (Altiplano). Therefore, the existence of additional inflows outside the basin is unlikely.

Optimization of phosphate removal in anodizing aluminium wastewater.

The wastewater produced after brightening and anodizing aluminium has high concentrations of phosphates and sulphates. The addition of MgO in a first physico-chemical wastewater treatment step makes the selective recovery of phosphates in the form of magnesium phosphates feasible, which may be reused as fertilizer. The proposed wastewater treatment process allows manufacturers to reduce more than 70% of the volume of the precipitate in the sedimentation reactor and more than 50% of the weight of the final disposal sludge. In this study, the use of an alternative low-grade MgO (LG-MgO) as a source of magnesium, which is cheaper than pure MgO, is investigated. The phosphate concentration and pH of the treated wastewater is controlled by the formation and precipitation of newberyite or bobierrite as a function of the magnesium source added. According to experimental data, a reaction mechanism is proposed. Although LG-MgO reacts more slowly than pure MgO and it is necessary to add 3-4 times the stoichiometric amount, this procedure has considerable economic and technical advantages.

Water acidification trends in a reservoir of the Iberian Pyrite Belt (SW Spain).

Scarcity of waters is the main limiting factor of economic development in most arid and semi-arid regions worldwide. The construction of reservoirs may be an optimal solution to assure water availability if the drainage area shows low disturbances. This is the quandary of mining areas where economic development relies on water accessibility. Water acidification trends were investigated in the Sancho Reservoir (SW Spain) in the last 20 years. The acidity (pH3-5) and high dissolved metal concentrations (e.g., 4.4 mg/L of Al, 2.1mg/L of Mn, 1.9 mg/L of Zn) observed in the Sancho, together with the large volume stored (between 37 and 55 Mm(3)), makes this reservoir an extreme case of surface water pollution worldwide. A progressive acidification has been observed since 2003, as evidenced by decreasing pH values and increasing dissolved metal concentrations, especially noticeable after 2007. The increase in the net acidity in the reservoir originates from the higher input of metals and acidity due to the rebound effect after the mining closure in 2001. This trend was not detected in the river feeding the reservoir due to its great hydrological and hydrochemical variability, typical of the Mediterranean climate. Chemical analysis and absolute dating of sediments identified a progressive enrichment in S and metals (i.e., Fe, Zn Cu, Ni, Co and Cd) in the upper 20 cm, which reinforce the year 2002/03 as the onset of the acidification of the reservoir. The decrease of pH values from 4-5 to 3-4 occurred later than the increase in sulfate and metals due to pH-buffering by Al. The acid mine drainage (AMD) pressure has caused an increment of dissolved Fe and other metals, as well as a change in the pH buffering role, exerted now by Fe. These processes were simulated by PHREEQC, which confirms that the acidification trend will continue, causing pH values to reach 2.5 if AMD pressure persists.

A clay permeable reactive barrier to remove Cs-137 from groundwater: Column experiments.

Clay minerals are reputed sorbents for Cs-137 and can be used as a low-permeability material to prevent groundwater flow. Therefore, clay barriers are employed to seal Cs-137 polluted areas and nuclear waste repositories. This work is motivated by cases where groundwater flow cannot be impeded. A permeable and reactive barrier to retain Cs-137 was tested. The trapping mechanism is based on the sorption of cesium on illite-containing clay. The permeability of the reactive material is provided by mixing clay on a matrix of wood shavings. Column tests combined with reactive transport modeling were performed to check both reactivity and permeability. Hydraulic conductivity of the mixture (10(-4) m/s) was sufficient to ensure an adequate hydraulic performance of an eventual barrier excavated in most aquifers. A number of column experiments confirmed Cs retention under different flow rates and inflow solutions. A 1D reactive transport model based on a cation-exchange mechanism was built. It was calibrated with batch experiments for high concentrations of NH4+ and K+ (the main competitors of Cs in the exchange positions). The model predicted satisfactorily the results of the column experiments. Once validated, it was used to investigate the performance and duration of a 2 m thick barrier under different scenarios (flow, clay content, Cs-137 and K concentration).

The impact of the Aznalcóllar mine tailing spill on groundwater.

As a consequence of a mine tailing dam collapse on the 25th April 1998, more than 4000 ha of the Guadiamar riverflat and farmlands were flooded by 4 hm3 of sulphide slurry. A number of open wells (12 of the 47 analyzed) were also flooded and the water was contaminated. Before the spill, the groundwater in the aquifers was of calcium-carbonate and calcium-sulphate type, with moderate mineralisation and near neutral pH. With the exception of some of the wells close to the mine, this groundwater had a low concentration of the metals associated with the Aznalcóllar mine. After the flood the following metals had anomalous concentrations in well water: Zn, Mn, Pb, Co, Cd and Tl. Of these, Zn seems to be the best tracer of the contamination, owing to its high concentrations. During the 5 months following the spill, water from the unflooded wells did not show an increase in metal concentration. Apart from some exceptions in August, the metal concentration in the affected wells showed a progressive decrease reaching levels closer to those in the wells free from contamination. Nevertheless, in the following dry seasons the draw-down of the water level may lead to exposure and weathering of sulphides in the wells, which could cause an increase in pollution. Therefore, thorough cleaning of all highly contaminated wells is strongly recommended.

Groundwater chemistry of the Okélobondo uraninite deposit area (Oklo, Gabon): two-dimensional reactive transport modelling.

The stability of uranium-bearing minerals in natural environments is of interest to evaluate the feasibility of radioactive waste repositories. The uraninite bodies, UO2(s), in the Oklo district (Gabon) are the result of a natural fission process, which took place 1970 Ma ago. These deposits can be regarded as natural analogues for spent fuel. One of the uraninite bodies, the Okélobondo deposit, is located at a depth of 300 m. Groundwater samples from boreholes located at shallow depths (100-200 m) show neutral to basic pH, anoxic conditions (Eh = 0.10 to -0.05 V) and are saturated with respect to uraninite. In contrast, deeper samples collected in the vicinity of the ore body are oxidising (Eh = 0.32-0.47 V), slightly basic (pH = 7.0-8.5) and undersaturated with respect to uraninite. These oxidising conditions at depth, if present under repository conditions, may affect the stability of uranium oxide. In order to improve our understanding of the observed site geochemistry, the available information on the lithology and groundwater flow was integrated in a reactive transport model. The chemical composition and the pH-Eh values of the water sampled above and in the western side of the Okélobondo deposit can be explained by the interaction of meteoric recharge with pelites, dolomites and sandstones. The dissolution of Fe(II)-silicates and the oxidation of the Fe(II)-aqueous species maintained the pH-Eh distribution along the Fe(2+)-Fe(OH)3(am) equilibrium, with the result that uraninite does not dissolve. This may explain the lower uranium content in the water samples from pelites and dolomites above the Okélobondo deposit. The high Mn/Fe ratio and the high pH-Eh values of the water sampled at depth, close to the Okélobondo deposit, suggest a control by the Mn(2+)-MnOOH(s) equilibrium. This control is attributed to the dissolution of a large rhodochrosite, MnCO3(s), and manganite, MnOOH(s) deposit in the recharge area on the eastern side.

On the behavior of approaches to simulate reactive transport.

Two families of approaches exist to simulate reactive transport in groundwater: The Direct Substitution Approach (DSA), based on Newton-Raphson and the Picard or Sequential Iteration Approach (SIA). We applied basic versions of both methods to several test cases and compared both computational demands and quality of the solution for varying grid size. Results showed that the behavior of the two approaches is sensitive to both grid size and chemistry. As a general rule, the DSA is more robust than the SIA, in the sense that its convergence is less sensitive to time step size (any approach will converge given a sufficiently small time step). Moreover, the DSA leads to a better simulation of sharp fronts, which can only be reproduced with fine grids after many iterations when the SIA is used. As a consequence, the DSA runs faster than SIA in chemically difficult cases (i.e., highly non-linear and/or very retarded), because the SIA may require very small time steps to converge. On the other hand, the size of the system of equations is much larger for the DSA than for the SIA, so that its CPU time and memory requirements tend to be less favorable with increasing grid size. As a result, the SIA may become faster than the DSA for very large, chemically simple problems. The use of an iterative linear solver for the DSA makes its CPU time less sensitive to grid size.

Geochemical modeling of arsenic release from a deep natural solid matrix under alternated redox conditions.

Dissolved arsenic (As) concentrations detected in groundwater bodies of the Emilia-Romagna Region (Italy) exhibit values which are above the regulation limit and could be related to the natural composition of the host porous matrix. To support this hypothesis, we present the results of a geochemical modeling study reproducing the main trends of the dynamics of As, Fe, and Mn concentrations as well as redox potential and pH observed during batch tests performed under alternating redox conditions. The tests were performed on a natural matrix extracted from a deep aquifer located in the Emilia-Romagna Region (Italy). The solid phases implemented in the model were selected from the results of selective sequential extractions performed on the tested matrix. The calibrated model showed that large As concentrations have to be expected in the solution for low crystallinity phases subject to dissolution. The role of Mn oxides on As concentration dynamics appears significant in strongly reducing environments, particularly for large water-solid matrix interaction times. Modeled data evidenced that As is released firstly from the outer surface of Fe oxihydroxides minerals exhibiting large concentrations in water when persistent reducing conditions trigger the dissolution of the crystalline structure of the binding minerals. The presence of organic matter was found to strongly affect pH and redox conditions, thus influencing As mobility.

Nitrate attenuation potential of hypersaline lake sediments in central Spain: flow-through and batch experiments.

Complex lacustrine systems, such as hypersaline lakes located in endorheic basins, are exposed to nitrate (NO3(-)) pollution. An excellent example of these lakes is the hypersaline lake located in the Pétrola basin (central Spain), where the lake acts as a sink for NO3(-) from agricultural activities and from sewage from the surrounding area. To better understand the role of the organic carbon (Corg) deposited in the bottom sediment in promoting denitrification, a four-stage flow-through experiment (FTR) and batch experiments using lake bottom sediment were performed. The chemical, multi-isotopic and kinetic characterization of the outflow showed that the intrinsic NO3(-) attenuation potential of the lake bottom sediment was able to remove 95% of the NO3(-) input over 296days under different flow conditions. The NO3(-) attenuation was mainly linked with denitrification but some dissimilatory nitrate reduction to ammonium was observed at early days favored by the high C/N ratio and salinity. Sulfate reduction could be neither confirmed nor discarded during the experiments because the sediment leaching masked the chemical and isotopic signatures of this reaction. The average nitrogen reduction rate (NRR) obtained was 1.25mmold(-1)kg(-1) and was independent of the flow rate employed. The amount of reactive Corg from the bottom sediment consumed during denitrification was 28.8mmol, representing approximately 10% of the total Corg of the sediment (1.2%). Denitrification was produced coupled with an increase in the isotopic composition of both δ(15)N and δ(18)O. The isotopic fractionations (ε of (15)N-NO3(-) and (18)O-NO3(-)) produced during denitrification were calculated using batch and vertical profile samples. The results were -14.7‰ for εN and -14.5‰ for εO.

Denitrification in a hypersaline lake-aquifer system (Pétrola Basin, Central Spain): the role of recent organic matter and Cretaceous organic rich sediments.

Agricultural regions in semi-arid to arid climates with associated saline wetlands are one of the most vulnerable environments to nitrate pollution. The Pétrola Basin was declared vulnerable to NO3(-) pollution by the Regional Government in 1998, and the hypersaline lake was classified as a heavily modified body of water. The study assessed groundwater NO3(-) through the use of multi-isotopic tracers (δ(15)N, δ(34)S, δ(13)C, δ(18)O) coupled to hydrochemistry in the aquifer connected to the eutrophic lake. Hydrogeologically, the basin shows two main flow components: regional groundwater flow from recharge areas (Zone 1) to the lake (Zone 2), and a density-driven flow from surface water to the underlying aquifer (Zone 3). In Zones 1 and 2, δ(15)NNO3 and δ(18)ONO3 suggest that NO3(-) from slightly volatilized ammonium synthetic fertilizers is only partially denitrified. The natural attenuation of NO3(-) can occur by heterotrophic reactions. However, autotrophic reactions cannot be ruled out. In Zone 3, the freshwater-saltwater interface (down to 12-16 m below the ground surface) is a reactive zone for NO3(-) attenuation. Tritium data suggest that the absence of NO3(-) in the deepest zones of the aquifer under the lake can be attributed to a regional groundwater flow with long residence time. In hypersaline lakes the geometry of the density-driven flow can play an important role in the transport of chemical species that can be related to denitrification processes.

Metal cycling during sediment early diagenesis in a water reservoir affected by acid mine drainage.

The discharge of acid mine drainage (AMD) into a reservoir may seriously affect the water quality. To investigate the metal transfer between the water and the sediment, three cores were collected from the Sancho Reservoir (Iberian Pyrite Belt, SW Spain) during different seasons: turnover event; oxic, stratified period; anoxic and under shallow perennially oxic conditions. The cores were sliced in an oxygen-free atmosphere, after which pore water was extracted by centrifugation and analyzed. A sequential extraction was then applied to the sediments to extract the water-soluble, monosulfide, low crystallinity Fe(III)-oxyhydroxide, crystalline Fe(III)-oxide, organic, pyrite and residual phases. The results showed that, despite the acidic chemistry of the water column (pH<4), the reservoir accumulated a high amount of autochthonous organic matter (up to 12 wt.%). Oxygen was consumed in 1mm of sediment due to organic matter and sulfide oxidation. Below the oxic layer, Fe(III) and sulfate reduction peaks developed concomitantly and the resulting Fe(II) and S(II) were removed as sulfides and probably as S linked to organic matter. During the oxic season, schwertmannite precipitated in the water column and was redissolved in the organic-rich sediment, after which iron and arsenic diffused upwards again to the water column. The flux of precipitates was found to be two orders of magnitude higher than the aqueous one, and therefore the sediment acted as a sink for As and Fe. Trace metals (Cu, Zn, Cd, Pb, Ni, Co) and Al always diffused from the reservoir water and were incorporated into the sediments as sulfides and oxyhydroxides, respectively. In spite of the fact that the benthic fluxes estimated for trace metal and Al were much higher than those reported for lake and marine sediments, they only accounted for less than 10% of their total inventory dissolved in the column water.

Biogenic hydroxyapatite (Apatite II™) dissolution kinetics and metal removal from acid mine drainage.

Apatite II™ is a biogenic hydroxyapatite (expressed as Ca(5)(PO(4))OH) derived from fish bone. Using grains of Apatite II™ with a fraction size between 250 and 500 µm, batch and flow-through experiments were carried out to (1) determine the solubility constant for the dissolution reaction Ca(5)(PO(4))(3)(OH) ⇔ 5Ca(2+) + 3PO(4)(3-) + OH(-), (2) obtain steady-state dissolution rates over the pH range between 2.22 and 7.14, and (3) study the Apatite II™'s mechanisms to remove Pb(2+), Zn(2+), Mn(2+), and Cu(2+) from metal polluted water as it dissolves. The logK(S) value obtained was -50.8±0.82 at 25 °C. Far-from-equilibrium fish-bone hydroxyapatite dissolution rates decrease by increasing pH. Assuming that the dissolution reaction is controlled by fast adsorption of a proton on a specific surface site that dominates through the pH range studied, probably ≡PO(-), followed by a slow hydrolysis step, the dissolution rate dependence is expressed in mol m(-2) s(-1) as where Rate(25 °C) = -8.9 × 10(-10) × [9.96 × 10(5) × a(H+)]/[1 + 9.96 × 10(5) × a(H+)] where a(H+) is the proton activity in solution. Removal of Pb(2+), Zn(2+), Mn(2+) and Cu(2+) was by formation of phosphate-metal compounds on the Apatite II™ substrate, whereas removal of Cd(2+) was by surface adsorption. Increase in pH enhanced the removal of aqueous heavy metals. Using the kinetic parameters obtained (e.g., dissolution rate and pH-rate dependence law), reactive transport simulations reproduced the experimental variation of pH and concentrations of Ca, P and toxic divalent metal in a column experiment filled with Apatite II™ that was designed to simulate the Apatite II™-metal polluted water interaction.

Geochemical and environmental controls on the genesis of soluble efflorescent salts in coastal mine tailings deposits: a discussion based on reactive transport modeling.

Water-soluble efflorescent salts often form on tailings in hyperarid climates. Their high solubility together with the high risk of human exposure to heavy metals such as Cu, Ni, Zn, etc., makes this occurrence a serious environmental problem. Understanding their formation (genesis) is therefore key to designing prevention and remediation strategies. A significant amount of these efflorescences has been described on the coastal area of Chañaral (Chile). There, highly soluble salts such as halite (NaCl) and eriochalcite (CuCl(2).2H(2)O) form on 4km(2) of marine shore tailings. Natural occurrence of eriochalcite is rare: its formation requires extreme environmental and geochemical conditions such as high evaporation rate and low relative air humidity, and continuous Cl and Cu supply from groundwater, etc. Its formation was examined by means of reactive transport modeling. A scenario is proposed involving sea water and subsequently a mixture of sea water/freshwater in the groundwater composition in the formation of these efflorescences. The strong competition from other halides (i.e. halite and silvite (KCl)) for the Cl may inhibit the precipitation of eriochalcite. Therefore, the Cl/Na ratio trend >1 is a key parameter in its formation. Cation-exchange between Na(+) and other major ions such as K(+), Ca(2+), Mg(2+) and Cu(2+) in the clay fraction of tailings is proposed to account for realistic Cl/Na ratios. With regard to preventing the formation of eriochalcite, a capillary barrier on the tailings surface is proposed as a suitable alternative. Its efficiency as a barrier is also tested by means of reactive transport models.