Laura Galván

Enrichment of rare earth elements as environmental tracers of contamination by acid mine drainage in salt marshes: A new perspective

Rare earth elements (REE) were analyzed in surface sediments from the Guadiana Estuary (SW Iberian Pyrite Belt). NASC (North American Shale Composite) normalized REE patterns show clearly convex curvatures in middle-REE (MREE) with respect to light- and heavy-REE, indicating acid-mixing processes between fluvial waters affected by acid mine drainage (AMD) and seawater. However, REE distributions in the mouth (closer to the coastal area) show slightly LREE-enriched and flat patterns, indicating saline-mixing processes typical of the coastal zone. NASC-normalized ratios (La/Gd and La/Yb) do not discriminate between both mixing processes in the estuary. Instead, a new parameter (E(MREE)) has been applied to measure the curvature in the MREE segment. The values of E(MREE)>0 are indicative of acid signatures and their spatial distribution reveal the existence of two decantation zones from flocculation processes related to drought periods and flood events. Studying REE fractionation through the E(MREE) may serve as a good proxy for AMD-pollution in estuarine environments in relation to the traditional methods.

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.

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.

Assessment of the dissolved pollutant flux of the Odiel River (SW Spain) during a wet period

The abandoned mining districts of the Iberian Pyrite Belt (IPB, SW Spain) are an extreme source of pollution by acid mine drainage (AMD) to the Tinto and Odiel rivers. The pollutant flux transported by the Odiel River during a high stage period was assessed using concentration-discharge relationships and concentration-conductivity relationships, for the hydrological year 2009/10 (which was especially wet). Both correlations were high (R(2)>0.80) for most of the elements studied. The two methods for flux calculation gave similar results with differences generally lower than 10%. The dissolved contaminant flux transported by the Odiel River just before its mouth mainly includes sulphate (257,534±13,464 t/yr), Al (13,259±1071 t/yr), Zn (4265±242 t/yr), Mn (2532±146 t/yr) and Cu (1738±136 t/yr), and minor amounts of other elements. These findings confirm that, up to our knowledge, the Odiel River can be considered to be the largest contributor of mining-related pollutants to the worlds oceans.

Oxycline formation induced by Fe(II) oxidation in a water reservoir affected by acid mine drainage modeled using a 2D hydrodynamic and water quality model — CE-QUAL-W2

The Sancho reservoir is an acid mine drainage (AMD)-contaminated reservoir located in the Huelva province (SW Spain) with a pH close to 3.5. The water is only used for a refrigeration system of a paper mill. The Sancho reservoir is holomictic with one mixing period per year in the winter. During this mixing period, oxygenated water reaches the sediment, while under stratified conditions (the rest of the year) hypoxic conditions develop at the hypolimnion. A CE-QUAL-W2 model was calibrated for the Sancho Reservoir to predict the thermocline and oxycline formation, as well as the salinity, ammonium, nitrate, phosphorous, algal, chlorophyll-a, and iron concentrations. The version 3.7 of the model does not allow simulating the oxidation of Fe(II) in the water column, which limits the oxygen consumption of the organic matter oxidation. However, to evaluate the impact of Fe(II) oxidation on the oxycline formation, Fe(II) has been introduced into the model based on its relationship with labile dissolved organic matter (LDOM). The results show that Fe oxidation is the main factor responsible for the oxygen depletion in the hypolimnion of the Sancho Reservoir. The limiting factors for green algal growth have also been studied. The model predicted that ammonium, nitrate, and phosphate were not limiting factors for green algal growth. Light appeared to be one of the limiting factors for algal growth, while chlorophyll-a and dissolved oxygen concentrations could not be fully described. We hypothesize that dissolved CO2 is one of the limiting nutrients due to losses by the high acidity of the water column. The sensitivity tests carried out support this hypothesis. Two different remediation scenarios have been tested with the calibrated model: 1) an AMD passive treatment plant installed at the river, which removes completely Fe, and 2) different depth water extractions. If no Fe was introduced into the reservoir, water quality would significantly improve in only two years. Deeper extractions (3m above the bottom) would also improve the water quality by decreasing the hypoxic zone. However, extractions at the epilimnion would increase the amount of hypoxic water in the reservoir.