| 1. |
- Antelo, Juan, et al.
(author)
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Stability of naturally occurring AMD–schwertmannite in the presence of arsenic and reducing agents
- 2021
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In: Journal of Geochemical Exploration. - : Elsevier. - 0375-6742 .- 1879-1689. ; 220
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Journal article (peer-reviewed)abstract
- Secondary iron oxides formed in acid mine drainage, such as schwertmannite, are scavengers for metal(loid)s in mining environments. Increasing the understanding of the geochemical transformations of these minerals, as well as knowing how metal(loid)s affect these transformations, is crucial to ultimately predict the fate of these trace elements in acidic mine drainage and to minimize the potential environmental risk. In this study, transformation experiments have been conducted with a schwertmannite-rich sediment collected from a mining area and with synthesized schwertmannite as a reference material. The transformation of schwertmannite into goethite was studied as a function of the presence of arsenic, pH value, and redox conditions. Arsenic delayed the mineral transformation from pseudo-stable amorphous phases to more stable crystalline forms, especially at higher arsenic loadings and more acidic pH. Experiments in the presence of Fe(II) and ascorbic acid have proven that both components promote the mineral transformation or reductive dissolution of schwertmannite under anoxic conditions. The presence of arsenic reduced the catalytic effect of Fe(II), stabilizing the schwertmannite particles. On the other hand, arsenic had no effect on the reductive dissolution at these conditions when ascorbic acid was used as a reducing agent. © 2020 Elsevier B.V.
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| 2. |
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| 3. |
- Carabante, Ivan, et al.
(author)
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Adsorption of As (V) on iron oxide nanoparticle films studied by in situ ATR-FTIR spectroscopy
- 2009
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In: Colloids and Surfaces A. - : Elsevier BV. - 0927-7757 .- 1873-4359. ; 346:1-3, s. 106-113
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Journal article (peer-reviewed)abstract
- Stabilization of arsenic contaminated soils by iron oxides has been proposed as a remediation technique to prevent leaching of arsenate into the environment. Fundamental studies are needed to establish under which conditions the complexes formed are stable. In the present work, a powerful technique, viz. ATR-FTIR spectroscopy, is adapted to studies of adsorption of arsenate species on iron oxides. This technique facilitates acquisition of both quantitative and qualitative in situ adsorption data.In the present work, about 800 nm thick films of 6-lineferrihydrite were deposited on ZnSe ATR crystals. Arsenate adsorption on the ferrihydrite film was studied at pD values ranging from 4 to 12 and at an arsenate concentration of 0.03 mM in D2O solution. The amount of adsorbed arsenate decreased with increasing pD as a result of the more negatively charged iron oxide surface at higher pD values. The adsorption and desorption kinetics were also studied. Arsenate showed a higher adsorption rate within the first 70 minutes and a much lower adsorption rate from 70 up to 300 minutes. The low adsorption rate at longer reaction times was partly due to a low desorption rate of already adsorbed carbonate species adsorbed at the surface. The desorption of carbonate species was evidenced by the appearance of negative absorption bands. The desorption of adsorbed arsenate complexes was examined by flushing with D2O at pD 4 and 8.5 and it was found that the complexes were very stable at pD 4 suggesting formation of mostly inner-sphere complexes whereas a fraction of the complexes at pD 8.5 were less stable than at pD 4, possibly due to the formation of outer-sphere complexes.In summary, the ATR technique was shown to provide in situ information about the adsorption rate, desorption rate and the speciation of the complexes formed within a single experiment, which is very difficult to obtain using other techniques.
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| 4. |
- Carabante, Ivan
(author)
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Arsenic (V) adsorption on iron oxide : implications for soil remedeation and water purification
- 2012
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Doctoral thesis (other academic/artistic)abstract
- Addition of iron oxide based adsorbents to arsenic contaminated soils has been proposed as a mean to reduce the mobility of arsenic in the soil. However, the conditions in the soil such as pH value, the presence of phosphate after addition of fertilizer to the soil or the presence of Zn (II) as a co-contaminant may affect the adsorption of arsenate on the iron oxide and may therefore have implications for the mobility of arsenic in the remediated soil.In the present work, a new flow method was developed to study the adsorption of arsenate on synthetic iron oxide with high surface area (ferrihydrite) in situ by means of Attenuated Total Reflection – Fourier Transform Infrared (ATR – FTIR) spectroscopy and the method was used for studying how the adsorption of arsenate was affected by the pH/pD value, the presence of phosphate and Zn (II) in the system. The highest adsorption of arsenate was found at pD 4 and decreased as the pD value increased. The arsenate complexes formed on ferrihydrite appeared to be very stable at pD 4, while the stability decreased as the pD value increased. Arsenate showed a higher adsorption affinity than phosphate on ferrihydrite under the conditions studied. However, phosphate was able to replace about 10 % of pre-adsorbed arsenate on ferrihydrite at pD 4 and about 20 % of the pre-adsorbed arsenate at pD 8.5 in equimolar concentrations of phosphate and arsenate. Phosphate replaced 30 % of pre-adsorbed arsenate at pD 4 and up to 50 % of pre-adsorbed arsenate at pD 8.5 when the concentration of phosphate in the system was 5 times higher than that of arsenate. Batch adsorption experiments indicated an enhancement in the arsenate removal from a ferrihydrite suspension in the presence of Zn (II) at pH 8 in accordance with previous reports. However, no adsorption of arsenate on ferrihydrite in the presence of high concentrations of Zn (II) in the system was observed by infrared spectroscopy. Instead, precipitation of zinc hydroxide carbonate followed by arsenate adsorption on the zinc precipitate was found to be the most likely explanation of these results.Although iron oxides are selective towards arsenate, high specific surface areas are required to achieve sufficiently high adsorption capacity. A method of increasing the specific surface area of coarse hematite particles to obtain a good adsorbent was also developed in the present work. The method comprises an acid treatment to produce iron ions followed by hydrolysis to precipitate an iron oxy-hydroxide coating on the hematite particles. While the arsenate adsorption capacity of the original coarse hematite particles was found to be negligible, the sintered coarse hematite particles showed good potential as an adsorbent for arsenate with an adsorption capacity of about 0.65 mg[As]/g.The method developed for studying adsorption on iron oxides by in situ ATR - FTIR spectroscopy was further developed for studying the adsorption of flotation collectors on iron oxides. Iron ore is often separated from gangue minerals by means of reverse flotation in which a surfactant should selectively adsorb on the gangue mineral rendering it hydrophobic. However, unwanted adsorption of the surfactants on the iron oxide has been reported to affect the production of iron ore pellets. A method was developed to study the adsorption of the surfactant Atrac 1563 on synthetic hematite in situ by means of ATR - FTIR spectroscopy. The adsorption of Atrac 1563 on hematite at pH 8.5 was found to mostly occur via interactions between the polar ester and ethoxy groups of the surfactant and the hematite surface.
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| 5. |
- Carabante, Ivan, et al.
(author)
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In situ ATR-FTIR studies on the competitive adsorption of arsenate and phosphate on ferrihydrite
- 2010
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In: Journal of Colloid and Interface Science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 351:2, s. 523-531
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Journal article (peer-reviewed)abstract
- In the present study, in-situ ATR-FTIR spectroscopy was used for the first time to study the competitive adsorption of phosphate and arsenate on ferrihydrite. Deuterium oxide was used as solvent to facilitate the interpretations of recorded infrared spectra.It was found that arsenate and phosphate adsorbed more strongly at lower pD values, showing similarities in the adsorption behavior as a function of pD. However, arsenate complexes were found to be more strongly adsorbed than phosphate complexes in the pD range studied. About five times higher concentration of phosphate in solution was needed to reduce the absorbance due to pre-adsorbed arsenate to the same relative level as for pre-adsorbed phosphate, which was desorbed using a solution containing equal (molar) concentrations in arsenate and phosphate. At pD 4, two phosphate complexes were adsorbed on the iron oxide, one deuterated and one de-deuterated. When phosphate was pre-adsorbed and arsenate subsequently added to the system, the deuterated phosphate complex desorbed rapidly while the de-deuterated phosphate complex was quite stable. At pD 8.5, only the de-deuterated phosphate complex was adsorbed on the iron oxide. Moreover, the arsenate adsorbed was also predominantly de-deuterated as opposite to the arsenate adsorbed at pD 4. During the substitution experiments the configuration of these complexes on the iron oxide surface did not change. To the best of our knowledge, this is the first time this difference in stability of the different phosphate complexes is reported and shows the power of employing in-situ spectroscopy for this kind of studies.
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| 6. |
- Carabante, Ivan, et al.
(author)
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Influence of Zn(II) on the adsorption of arsenate onto ferrihydrite
- 2012
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In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 46:24, s. 13152-13159
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Journal article (peer-reviewed)abstract
- Addition of iron oxide to arsenic-contaminated soil has been proposed as a means of reducing the mobility of arsenic in the soil. Arsenic and zinc are common coexisting contaminants in soils. The presence of zinc therefore may affect the adsorption properties of arsenic on iron oxide, and may thus affect its mobility in the soil. The influence of Zn(II) on the adsorption of arsenate ions on iron oxide was studied. Batch adsorption experiments indicated that Zn(II) increased the arsenate removal from a solution by ferrihydrite at pH 8. However, ATR-FTIR spectroscopy showed that no adsorption of arsenate on a ferrihydrite film occurred at pD 8 in the presence of Zn(II). Precipitation of zinc hydroxide carbonate followed by arsenate adorption onto the precipitate was found to be a plausible mechanism explaining the arsenate removal from a solution in the presence of Zn(II) at pH/pD 8. The previously suggested mechanisms attributing the enhanced removal of arsenate from solution in the presence of Zn(II) to additional adsorption on iron oxides could not be verified under the experimental conditions studied. It was also shown that at pH/pD 4, the presence of Zn(II) in the system did not significantly affect the adsorption of arsenate on ferrihydrite.
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| 7. |
- Carabante, Ivan, et al.
(author)
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Reciprocal influence of arsenic and iron on the long-term immobilization of arsenic in contaminated soils
- 2018
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In: Environmental Arsenic in a Changing World. - London : Taylor & Francis. ; , s. 467-469
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Conference paper (peer-reviewed)abstract
- The main aim of this work was to evaluate the fate of arsenic associated with iron minerals in contaminated soils. The ageing behavior of synthetic arsenic-bearing poorly crystalline minerals – ferrihydrite and schwertmannite – was studied. Arsenic showed a passivation effect on poorly crystalline minerals, delaying their transformation towards more crystalline iron oxides. These results agreed well with studies performed on contaminated soils and sediments. These results are relevant in order to understand the long-term mobility of arsenic in contaminated soils and sediments. Iron oxides sequesters arsenic efficiently and, reciprocally, arsenic stabilize the mineral, delaying its transformation towards more crystalline phases.
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| 8. |
- Carabante, Ivan, et al.
(author)
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Reutilization of porous sintered hematite bodies as effective adsorbents for arsenic(V) removal from water
- 2014
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In: Industrial & Engineering Chemistry Research. - : American Chemical Society (ACS). - 0888-5885 .- 1520-5045. ; 53:32, s. 12689-12696
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Journal article (peer-reviewed)abstract
- A method was developed to enhance the arsenic adsorption capacity of porous bodies of sintered hematite. The method comprised the formation of a coating of 1 wt % iron oxide nanoparticles on the raw material. The nanoparticles showed two distinct habits: spherical habit, likely ferrihydrite, and acicular habit, likely goethite and/or akaganéite. The specific surface area of the hematite raw material increased from 0.5 to 3.75 m2/g, and the adsorption capacity increased from negligible to 0.65 mg of [As]/g as calculated from equilibrium and breakthrough adsorption data. Equilibrium adsorption data of arsenate on the adsorbent from a solution at pH 5 followed the Langmuir model, while breakthrough adsorption data for a 500 μg/L arsenate solution at pH 5 followed the Thomas model. The adsorbed arsenic could be desorbed using distilled water at pH 12. These results show the potential for the reutilization of waste products comprising coarse hematite bodies as adsorbents.
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| 9. |
- Carabante, Ivan
(author)
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Study of arsenate adsorption on iron oxide by in situ ATR-FTIR spectroscopy
- 2009
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Licentiate thesis (other academic/artistic)abstract
- Stabilization of arsenic contaminated soils by iron oxides has been proposed as a remediation technique to prevent leaching of arsenate into the environment. However, fundamental studies are needed to establish under which conditions the complexes formed are stable. A new method based on ATR-FTIR spectroscopy was adapted to study the adsorption of arsenate species on iron oxides. The measurements required the use of D2O as solvent. The amount of arsenate complexes adsorbed on the iron oxide increased with decreasing pD in the range studied, viz. pD 4-12. Arsenate complexes adsorbed at pD 4 desorbed from the film to some extent as the pD was increased to 8.5 or 12. The stability of arsenate complexes adsorbed on the iron oxide evidently changed with the change in pD, most likely due to the electrostatic repulsion between the negatively charged oxoanion and the more negatively charged iron oxide as the pD increased. From competitive adsorption experiments it was found that arsenate species were more strongly bonded to the iron oxide than phosphate species. Furthermore, it was found that two different phosphate complexes formed on the iron surface at pD 4, one deuterated and the other one de-deuterated. The complexes showed very different stability. The deuterated phosphate complex was desorbed easily from the iron oxide film as arsenate was added to the system whereas the de-deuterated phosphate complex only desorbed slightly from the film upon adding arsenate.This work has increased the fundamental knowledge of the iron oxide/arsenate/phosphate system, which will be of importance for the development of more effective soil remediation techniques.
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| 10. |
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