Fernando Garrido

Thallium occurrence and partitioning in soils and sediments affected by mining activities in Madrid province (Spain)

Thallium (Tl) and its compounds are toxic to biota even at low concentrations but little is known about Tl concentration and speciation in soils. An understanding of the source, mobility, and dispersion of Tl is necessary to evaluate the environmental impact of Tl pollution cases. In this paper, we examine the Tl source and dispersion in two areas affected by abandoned mine facilities whose residues remain dumped on-site affecting to soils and sediments of natural water courses near Madrid city (Spain). Total Tl contents and partitioning in soil solid phases as determined by means of a sequential extraction procedure were also examined in soils along the riverbeds of an ephemeral and a permanent streams collecting water runoff and drainage from the mines wastes. Lastly, electronic microscopy and cathodoluminescence probe are used as a suitable technique for Tl elemental detection on thallium-bearing phases. Tl was found mainly bound to quartz and alumino-phyllosilicates in both rocks and examined soils. Besides, Tl was also frequently found associated to organic particles and diatom frustules in all samples from both mine scenarios. These biogenic silicates may regulate the transfer of Tl into the soil-water system.

COMPARISON OF TIME DOMAIN REFLECTOMETRY, FIBER OPTIC MINI-PROBES, AND SOLUTION SAMPLERS FOR REAL TIME MEASUREMENT OF SOLUTE TRANSPORT IN SOIL

Characterizing water and solute transport in soil requires sampling at a scale and temporal resolution appropriate for the question being studied. Sampling scale is also an important factor to consider when using devices to obtain transport parameters for modeling. In fact, probes that monitor solute transport at different sample volumes may actually produce dissimilar results; consequently, it is necessary to understand how devices produce different breakthrough curves (BTCs). Three in situ nondestructive methods to monitor solute transport were tested and compared in a single repacked clay loam soil column. The methods compared included time domain reflectometry (TDR), fiber optic miniprobes (FOMP), and continuous pore water small tube samplers (STS). All three probes-TDR, FOMP, and STS-performed well in measuring solute transport in the soil column. We found that a single point linear calibration is sufficient to correlate concentration to electrical conductivity for horizontally inserted TDR probes. In addition, the convective dispersive equation (CDE) described adequately the BTC measured with TDR, FOMP, and STS. The average effective pore water velocity, estimated by fitting the data to the CDE, were similar for all of the probes. Finally, we point out that effective dispersion values estimated using data from each type of probe were systematically different. This difference may be an artifact of a lower mass balance resulting from the calibration procedures, a scale issue resulting from the probe sampling volumes, or both. Nevertheless, the fit from each probe produced a different transport parameter for effective dispersion, and this must be considered when comparing results obtained with different monitoring devices.

Spread and partitioning of arsenic in soils from a mine waste site in Madrid province (Spain)

The formation of scorodite is an important mechanism for the natural attenuation of arsenic in a wide range of environments. It is dumped on site by metallurgical industries to minimize arsenic release. However, the long-term stability of these deposits is unclear. Sequential As extractions and synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy were used to determine both As and Fe speciation in a small catchment area affected by a scorodite-rich waste pile at an abandoned smelting factory. Our results indicate that this deposit behaves as an acute point source of As and metal pollution and confirms the strong association of As(V) with Fe(III) oxide phases, highlighting the important role of ferrihydrite as an As scavenger in natural systems. In this seasonally variable system, other trapping forms such as jarosite-like minerals also play a role in the attenuation of As. Overall, our results demonstrate that scorodite should not be considered an environmental stable repository for As attenuation when dumped outside because natural rainfall and the resulting runoff drive As dispersion in the environment and indicate the need to monitor and reclamate As-rich mine deposits.

Arsenic speciation in the dispersible colloidal fraction of soils from a mine-impacted creek

Arsenic and iron speciation in the dispersible colloid fraction (DCF; 10-1000 nm) from an As-rich mine waste pile, sediments of a streambed that collects runoff from waste pile, the streambed subsoil, and the sediments of a downstream pond were investigated by combining asymmetrical-flow field-flow fractionation (AsFlFFF)/inductively-coupled plasma-mass spectrometry (ICP-MS), transmission electron microscopy (TEM) and X-ray absorption (XAS) spectroscopy. Calcium, Fe and As (Fe/As molar ratio ∼ 1) were the main components of the DCF from waste pile. TEM/EDS and As and Fe XAS analysis revealed the presence of nanoparticle scorodite in this same DCF, as well as Fe nanoparticles in all samples downstream of the waste pile. Arsenic and Fe XAS showed As(V) adsorbed onto nanoparticulate ferrihydrite in the DCF of downstream samples. Micro-X-ray fluorescence indicated a strong correlation between Fe and As in phyllosilicate/Fe(3+) (oxi) hydroxide aggregates from the sediment pond. Fractionation analysis showed the mean particle size of the DCF from the streambed sample to be smaller than that of the streambed subsoil and sediment ponds samples. These results show that an important and variable fraction of As may be bound to dispersible colloids that can be released from contaminated soils and transported downstream in natural systems.

Potential use of gypsum and lime rich industrial by-products for induced reduction of Pb, Zn and Ni leachability in an acid soil

This study evaluates the potential use of four industrial by-products (phosphogypsum (PG), red gypsum (RG), sugar foam (SF), and ashes from biomass combustion (ACB)), applied at two rates in single and combined amendments to reduce the mobility and availability of Pb, Zn and Ni in a metal-spiked acid soil. Leaching experiments were done to estimate leachability indexes and assess their effectiveness. Most of the treatments significantly reduced the metal leachability although only a few were effective for all metals. Based on principal component and cluster analysis, sugar foam (SF) and a mixture of RG and ACB (RG+ACB), both applied at high rate, were selected as first choices to reduce mobility and availability of the three metals. Metal sorption mechanisms involved in the reduction of their leachability were identified using scanning electron microscopy. In the SF-treated samples, the metals were found associated to amorphous Al-hydroxy polymers deposited on phyllosilicates and organic matter particles. In the (RG+ACB)-treated samples, Pb, Zn, and traces of Ni were found associated to Fe/Ti oxide phases with a significant concentration of S, suggesting the formation of metal-sulfate ternary complexes.

Colloidal mobilization of arsenic from mining-affected soils by surface runoff.

Scorodite-rich wastes left as a legacy of mining and smelting operations pose a threat to environmental health. Colloids formed by the weathering of processing wastes may control the release of arsenic (As) into surface waters. At a former mine site in Madrid (Spain), we investigated the mobilization of colloidal As by surface runoff from weathered processing wastes and from sediments in the bed of a draining creek and a downstream sedimentation-pond. Colloids mobilized by surface runoff during simulated rain events were characterized for their composition, structure and mode of As uptake using asymmetric flow field-flow fractionation coupled to inductively plasma mass spectrometry (AF4-ICP-MS) and X-ray absorption spectroscopy (XAS) at the As and Fe K-edges. Colloidal scorodite mobilized in surface runoff from the waste pile is acting as a mobile As carrier. In surface runoff from the river bed and the sedimentation pond, ferrihydrite was identified as the dominant As-bearing colloidal phase. The results from this study suggest that mobilization of As-bearing colloids by surface runoff may play an important role in the dispersion of As from metallurgical wastes deposited above ground and needs to be considered in risk assessment.

Effect of the addition of industrial by-products on Cu, Zn, Pb and As leachability in a mine sediment.

A series of incubation and leaching experiments were performed to assess the feasibility of three industrial by-products (red gypsum (RG), sugar foam (SF) and ashes from the combustion of biomass (ACB)) to reduce the leachability of Cu, Pb, Zn and As in a sediment of São Domingos mine (Portugal). The changes in the element solid phase speciation were also evaluated by applying a sequential extraction procedure. All amendments significantly reduced the leachability of Zn and Cu, whereas the treatment with RG+SF+ACB also decreased the mobility of As. The reduction in Cu leachability was especially remarkable. This could be due to the great affinity of carbonates (included in SF and SF+ACB amendments) to precipitate with Cu, and maghemite and rutile (RG amendment) for acting as relevant sorbents for Cu. Pb was the least mobile element in the sediment and none of the treatments reduced its mobility. The sequential extraction reveals that the amendments induced a significant decrease in the concentration of elements associated with the residual fraction. Cu, Pb and As are redistributed from the residual fraction to the Al, Fe, and Mn hydr(oxides) fraction and Zn from the residual fraction to the water/acid soluble, exchangeable and bound to carbonates pool.

Assessment of the use of industrial by-products for induced reduction of As, and Se potential leachability in an acid soil

Four industrial by-products (phosphogypsum, PG; red gypsum, RG; sugar foam, SF and ashes from the combustion of biomass, ACB) were evaluated as possible amendments for reducing the leachability and bioavailability of As and Se in a metalloid-spiked acidic soil. The treatments were applied as single, double and triple amendments and at two different rates. The effectiveness of the treatments was evaluated after a series of leaching experiments using a chelating agent (DTPA solution) or a weak acidification (acetic acid at pH 4.93). The most effective treatments (ACB and RG, both applied at high rate) were identified by means of Cluster Analysis using the leachability indexes. Different sorption mechanisms involved in the overall reduction of metalloid leachability were identified using scanning electron microscopy (SEM-BSE and SEM-EDS). In the ACB-treated samples, Se was found associated to organic matter aggregates and to Fe compounds. In the RG-treated samples, EDS analyses showed that As and Se were associated to Fe/Ti (hydr)oxides phases which are present not only in the by-product as maghemite and rutile, but also in the soil as hematite and goethite. In addition, the application of RG induced the formation of non-crystalline Al-hydroxy polymers with As and Se in their composition.

Fractionation and mobility of thallium in areas impacted by mining-metallurgical activities: Identification of a water-soluble Tl(I) fraction

Mining and metallurgy generate residues that may contain thallium (Tl), a highly toxic metal, for which it is currently not feasible to determine its geochemical speciation through X-ray absorption spectroscopy due to a combination of very low contents and the interference of accompanying high arsenic contents. Therefore, fractionation studies in residues and soils are required to analyze the mobility and bioavailability of this metal, which in turn provide information to infer its speciation. For this purpose, in this work a modification of the BCR procedure was applied to residues and contaminated soils from three mining zones of Mexico and two mining zones of Spain, spanning samples with acidic to alkaline pH values. The Tl extraction procedure consisted of the following fractions: (1) water-extractable, (2) easily exchangeable and associated to carbonates, associated to (3) poorly-crystalline and (4) crystalline Fe and Mn oxyhydroxides, and (5) associated to organic matter and sulfides; and finally a residual fraction as associated to refractory primary and other secondary minerals. The extracted contents were analyzed by Inductively-Coupled Plasma with Mass Spectrometry. Surprisingly, water-soluble, in Tl(I) oxidation state, was detected in most areas, regardless of the pH, a fact that has not been reported before in these environments, and alerts to potential health risks not previously identified. Most of the samples from a metallurgy area showed high levels of Tl in non-residual fractions and a strong correlation was obtained between extracted Mn and Tl in the third fraction, suggesting its association to poorly crystalline manganese oxides. In the majority of samples from purely mining environments, most of the Tl was found in the residual fraction, most probably bound to alumino-silicate minerals. The remaining Tl fractions were extracted mainly associated to the reducible mineral fractions, and in one case also in the oxidizable fraction (presumably associated to sulfides). Capsule: Soluble Tl(I) was found in all soil samples contaminated with either mining or metallurgical wastes. Additionally, in those affected by metallurgical wastes a very strong Tl-Mn correlation was found.

Temporal Consistency Of Solute Transport In A Heterogeneous Field Plot

Although the spatial variability of solute transport in field soils has been examined intensively, far less information is available about temporal changes in transport processes. If there are changes in transport over time, simply calibrating a model with a breakthrough curve for a single time period may not be adequate. Therefore, this paper examines the consistency in solute transport measurements in a field soil using two in situ nondestructive techniques: fiber optic miniprobes (FOMPs) and time domain reflectometry (TDR) probes. Miscible displacement studies were performed in a small field plot containing 20 FOMPs and 16 TDR probes placed at two soil depths. Whereas there was moderate consistency in transport response measured by the TDR probes, the FOMP data suggested that solute transport converged into fewer flow pathways over time with repeated leaching. The 5-cm-long TDR probes also provided evidence of increased lateral flow in the first 50 mm of soil with time. The temporal variability was surprisingly similar between the FOMPs and the TDR probes, even though their sampling volumes differ by more than four orders of magnitude. Relationships between probe responses within the plot were examined using a Spearmans rank test, confirming that transport response pattern may not be temporally stable. This paper demonstrates that solute breakthrough may not be consistent in heterogeneous field soils subjected to regular leaching.