TY  - JOUR
AU  - Antić-Mladenović, Svetlana
AU  - Frohne, Tina
AU  - Kresović, Mirjana
AU  - Staerk, Hans-Joachim
AU  - Tomić, Zorica
AU  - Ličina, Vlado
AU  - Rinklebe, Joerg
PY  - 2017
UR  - http://aspace.agrif.bg.ac.rs/handle/123456789/4371
AB  - The redox-induced (im)mobilization of nickel (Ni) and lead (Pb) under pre-definite redox conditions and their binding forms were studied in a periodically flooded, slightly acidic arable soil enriched with serpentine minerals at the Velika Morava River valley, Serbia. The total contents of Ni and Pb were 152 and 109 mg kg(-1), respectively. Geochemical fractionation of Ni, combined with mineralogical analysis, confirmed its geogenic origin in the soil. Potentially mobile fractions were the dominating binding forms of Pb; thus, indicating anthropogenic sources as prevailing. Risk assessment indicated a low risk of Ni and Pb transfer from soil to other environmental constituents. However, the results imply that geogenic metals might pose higher environmental risk than those from anthropogenic origin, in dependence of their total concentrations and contents in the specific solid-phase fractions. Flooding of the soil was simulated in an automated biogeochemical microcosm system, which allows a control and a continuous measurements of redox potential (En) and pH. Subsequently, the EH was increased in steps of approximately 100 mV from anoxic to oxic conditions. Concurrently, the concentrations of soluble Ni, Pb, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), and sulfates were measured. The EH was brought from low to high values (-220 to 520 mV) and correlated negative with soluble Ni, Pb, Fe, Mn and DOC. Soluble Ni ranged from 125 to 228 mu g 1(-1) while Pb ranged from 3.0 to 21.4 mu g 1(-1). Concentrations of both metals in solution were high at low EH and decreased with increasing EH. Nickel immobilization may be attributed to sorption to or co-precipitation with re-oxidized Fe-Mn (hydr)oxides, whereas Pb, in addition, might be immobilized via precipitation with inorganic ligands, such as carbonates and phosphates. The results imply that Ni and Pb solubility might also be related to the formation of metal-DOC complexes. The detected dynamic and mechanisms might be useful in providing critical information for assessing the potential environmental risk and creating appropriate environmental management strategies for agricultural areas enriched with Ni and Pb.
PB  - Academic Press Ltd- Elsevier Science Ltd, London
T2  - Journal of Environmental Management
T1  - Biogeochemistry of Ni and Pb in a periodically flooded arable soil: Fractionation and redox-induced (im)mobilization
EP  - 150
SP  - 141
VL  - 186
DO  - 10.1016/j.jenvman.2016.06.005
ER  - 

@article{
author = "Antić-Mladenović, Svetlana and Frohne, Tina and Kresović, Mirjana and Staerk, Hans-Joachim and Tomić, Zorica and Ličina, Vlado and Rinklebe, Joerg",
year = "2017",
abstract = "The redox-induced (im)mobilization of nickel (Ni) and lead (Pb) under pre-definite redox conditions and their binding forms were studied in a periodically flooded, slightly acidic arable soil enriched with serpentine minerals at the Velika Morava River valley, Serbia. The total contents of Ni and Pb were 152 and 109 mg kg(-1), respectively. Geochemical fractionation of Ni, combined with mineralogical analysis, confirmed its geogenic origin in the soil. Potentially mobile fractions were the dominating binding forms of Pb; thus, indicating anthropogenic sources as prevailing. Risk assessment indicated a low risk of Ni and Pb transfer from soil to other environmental constituents. However, the results imply that geogenic metals might pose higher environmental risk than those from anthropogenic origin, in dependence of their total concentrations and contents in the specific solid-phase fractions. Flooding of the soil was simulated in an automated biogeochemical microcosm system, which allows a control and a continuous measurements of redox potential (En) and pH. Subsequently, the EH was increased in steps of approximately 100 mV from anoxic to oxic conditions. Concurrently, the concentrations of soluble Ni, Pb, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), and sulfates were measured. The EH was brought from low to high values (-220 to 520 mV) and correlated negative with soluble Ni, Pb, Fe, Mn and DOC. Soluble Ni ranged from 125 to 228 mu g 1(-1) while Pb ranged from 3.0 to 21.4 mu g 1(-1). Concentrations of both metals in solution were high at low EH and decreased with increasing EH. Nickel immobilization may be attributed to sorption to or co-precipitation with re-oxidized Fe-Mn (hydr)oxides, whereas Pb, in addition, might be immobilized via precipitation with inorganic ligands, such as carbonates and phosphates. The results imply that Ni and Pb solubility might also be related to the formation of metal-DOC complexes. The detected dynamic and mechanisms might be useful in providing critical information for assessing the potential environmental risk and creating appropriate environmental management strategies for agricultural areas enriched with Ni and Pb.",
publisher = "Academic Press Ltd- Elsevier Science Ltd, London",
journal = "Journal of Environmental Management",
title = "Biogeochemistry of Ni and Pb in a periodically flooded arable soil: Fractionation and redox-induced (im)mobilization",
pages = "150-141",
volume = "186",
doi = "10.1016/j.jenvman.2016.06.005"
}

Antić-Mladenović, S., Frohne, T., Kresović, M., Staerk, H., Tomić, Z., Ličina, V.,& Rinklebe, J.. (2017). Biogeochemistry of Ni and Pb in a periodically flooded arable soil: Fractionation and redox-induced (im)mobilization. in Journal of Environmental Management
Academic Press Ltd- Elsevier Science Ltd, London., 186, 141-150.
https://doi.org/10.1016/j.jenvman.2016.06.005

Antić-Mladenović S, Frohne T, Kresović M, Staerk H, Tomić Z, Ličina V, Rinklebe J. Biogeochemistry of Ni and Pb in a periodically flooded arable soil: Fractionation and redox-induced (im)mobilization. in Journal of Environmental Management. 2017;186:141-150.
doi:10.1016/j.jenvman.2016.06.005 .

Antić-Mladenović, Svetlana, Frohne, Tina, Kresović, Mirjana, Staerk, Hans-Joachim, Tomić, Zorica, Ličina, Vlado, Rinklebe, Joerg, "Biogeochemistry of Ni and Pb in a periodically flooded arable soil: Fractionation and redox-induced (im)mobilization" in Journal of Environmental Management, 186 (2017):141-150,
https://doi.org/10.1016/j.jenvman.2016.06.005 . .

TY  - JOUR
AU  - Antić-Mladenović, Svetlana
AU  - Frohne, Tina
AU  - Kresović, Mirjana
AU  - Staerk, Hans-Joachim
AU  - Savić, Dubravka
AU  - Ličina, Vlado
AU  - Rinklebe, Joerg
PY  - 2017
UR  - http://aspace.agrif.bg.ac.rs/handle/123456789/4326
AB  - To our knowledge, this is the first work to mechanistically study the impact of the redox potential (EH) and principal factors, such as pH, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), chlorides (Cl-) and sulfates (SO42-), on the release dynamics of thallium (Tl) in periodically flooded soil. We simulated flooding using an automated biogeochemical microcosm system that allows for systematical control of pre-defined redox windows. The EH value was increased mechanistically at intervals of approximately 100 mV from reducing (-211 mV) to oxidizing (475 mV) conditions. Soluble Tl levels (0.02-0.28 mu g L-1) increased significantly with increases in E-H (r = 0.80, p  lt  0.01, n = 30). Thallium mobilization was found to be related to several simultaneous processes involving the gradual oxidation of Tl-bearing, sulfides, reductive dissolution of Fe-Mn oxides and desorption from mineral sorbents. Manganese oxides did not appear to have a considerable effect on Tl retention under oxidizing conditions. Before conducting the microcosm experiment, Tl geochemical fractionation was assessed using the modified BCR sequential extraction procedure. The BCR revealed a majority of Tl in the residual fraction (77.7%), followed by reducible (13.3%) and oxidizable fractions (5.9%). By generating high levels of Tl toxicity at low doses, Ti released under oxidizing conditions may pose an environmental threat. In the future, similar studies should be conducted on various soils along with a determination of the Tl species and monitoring of the Tl content in plants to achieve more detailed insight into soluble Tl behavior.
PB  - Pergamon-Elsevier Science Ltd, Oxford
T2  - Chemosphere
T1  - Redox-controlled release dynamics of thallium in periodically flooded arable soil
EP  - 276
SP  - 268
VL  - 178
DO  - 10.1016/j.chemosphere.2017.03.060
ER  - 

@article{
author = "Antić-Mladenović, Svetlana and Frohne, Tina and Kresović, Mirjana and Staerk, Hans-Joachim and Savić, Dubravka and Ličina, Vlado and Rinklebe, Joerg",
year = "2017",
abstract = "To our knowledge, this is the first work to mechanistically study the impact of the redox potential (EH) and principal factors, such as pH, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), chlorides (Cl-) and sulfates (SO42-), on the release dynamics of thallium (Tl) in periodically flooded soil. We simulated flooding using an automated biogeochemical microcosm system that allows for systematical control of pre-defined redox windows. The EH value was increased mechanistically at intervals of approximately 100 mV from reducing (-211 mV) to oxidizing (475 mV) conditions. Soluble Tl levels (0.02-0.28 mu g L-1) increased significantly with increases in E-H (r = 0.80, p  lt  0.01, n = 30). Thallium mobilization was found to be related to several simultaneous processes involving the gradual oxidation of Tl-bearing, sulfides, reductive dissolution of Fe-Mn oxides and desorption from mineral sorbents. Manganese oxides did not appear to have a considerable effect on Tl retention under oxidizing conditions. Before conducting the microcosm experiment, Tl geochemical fractionation was assessed using the modified BCR sequential extraction procedure. The BCR revealed a majority of Tl in the residual fraction (77.7%), followed by reducible (13.3%) and oxidizable fractions (5.9%). By generating high levels of Tl toxicity at low doses, Ti released under oxidizing conditions may pose an environmental threat. In the future, similar studies should be conducted on various soils along with a determination of the Tl species and monitoring of the Tl content in plants to achieve more detailed insight into soluble Tl behavior.",
publisher = "Pergamon-Elsevier Science Ltd, Oxford",
journal = "Chemosphere",
title = "Redox-controlled release dynamics of thallium in periodically flooded arable soil",
pages = "276-268",
volume = "178",
doi = "10.1016/j.chemosphere.2017.03.060"
}

Antić-Mladenović, S., Frohne, T., Kresović, M., Staerk, H., Savić, D., Ličina, V.,& Rinklebe, J.. (2017). Redox-controlled release dynamics of thallium in periodically flooded arable soil. in Chemosphere
Pergamon-Elsevier Science Ltd, Oxford., 178, 268-276.
https://doi.org/10.1016/j.chemosphere.2017.03.060

Antić-Mladenović S, Frohne T, Kresović M, Staerk H, Savić D, Ličina V, Rinklebe J. Redox-controlled release dynamics of thallium in periodically flooded arable soil. in Chemosphere. 2017;178:268-276.
doi:10.1016/j.chemosphere.2017.03.060 .

Antić-Mladenović, Svetlana, Frohne, Tina, Kresović, Mirjana, Staerk, Hans-Joachim, Savić, Dubravka, Ličina, Vlado, Rinklebe, Joerg, "Redox-controlled release dynamics of thallium in periodically flooded arable soil" in Chemosphere, 178 (2017):268-276,
https://doi.org/10.1016/j.chemosphere.2017.03.060 . .

TY  - JOUR
AU  - Rinklebe, Joerg
AU  - Antić-Mladenović, Svetlana
AU  - Frohne, Tina
AU  - Staerk, Hans-Joachim
AU  - Tomić, Zorica
AU  - Ličina, Vlado
PY  - 2016
UR  - http://aspace.agrif.bg.ac.rs/handle/123456789/4134
AB  - We determined redox-induced (im)mobilization of geogenic nickel (Ni) as well as binding forms of Ni in a Fluvisol at the River Velika Morava valley (Serbia), enriched with serpentine minerals. The selected site is representative for intensive agricultural land use in the area and susceptible to dynamic redox conditions due to periodical flooding. A seven-step sequential extraction, grain-size and light-liquid separation as well as mineralogical analyses were used, first, to assess binding forms of Ni and second, to determine relationships between grain-size fractions, abundance of heavy density minerals, and Ni concentration in the bulk soil. The sequential extraction revealed that the majority of Ni was in the residual fraction, followed by organic matter and Fe oxides. Fine grain-size fraction ( lt 63 mu m) was the major location of accumulation of Ni in the soil. Minerals which are characteristic for serpentine soils such as serpentine, spinels, hematite, and magnetite were found in silt and in the heavy density fraction (>2.9 g ml(-1)) of the medium and fine sand. However, the light minerals quartz, chlorite, micas, and secondary clay minerals dominate the soil mineral composition. Thus, total Ni concentration in the soil is derived from the content of Ni-bearing minerals and diluted by the minerals which are low in Ni. We simulated flooding using an automated biogeochemical microcosm system and determined the release dynamics of Ni at controlled redox potentials (E-H) in soil slurries. Pre-defined redox-windows were systematically created in steps of approximately 100 mV from reducing to oxidizing conditions while E-H and pH were continuously monitored. In parallel, the release dynamics of soluble nickel (Ni), iron (Fe), magnesium (Mg), manganese (Mn), dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), and sulfate (SO42-) were measured at each E-H-window. Our results highlighted that geogenic Ni can be mobilized to a considerable amount during low E-H, while elevating E-H from reducing to oxidizing conditions generated an immobilization Ni. We suggested that mobilization of Ni has been primarily affected by formation of Ni DOC complexes at low E-H, whereas Ni seems to be immobilized as a result of formation of Fe/Mn (hydro)oxides and the linked co-precipitation of Ni during oxidation. Factor analysis (FA) as multivariate statistical method explained 85.08% of the variance (67.89% and 17.19% component Nos. 1 and 2, respectively). The FA reveals that soluble Ni, Fe, DOC, Mn, and Mg were clustered in one group which indicate that the combined effect of DOC together with the chemistry of Fe, Mn, and Mg might be linked to the redox-induced release dynamics of Ni. The practical perspective of the study was to draw attention to dynamics of soluble Ni in fluctuating conditions for a better ecological risk assessment of floodplain sites under agricultural use. Nevertheless, similar studies should be conducted with further serpentine soils from various sites world-wide to verify the detected dynamics and processes.
PB  - Elsevier, Amsterdam
T2  - Geoderma
T1  - Nickel in a serpentine-enriched Fluvisol: Redox affected dynamics and binding forms
EP  - 214
SP  - 203
VL  - 263
DO  - 10.1016/j.geoderma.2015.09.004
ER  - 

@article{
author = "Rinklebe, Joerg and Antić-Mladenović, Svetlana and Frohne, Tina and Staerk, Hans-Joachim and Tomić, Zorica and Ličina, Vlado",
year = "2016",
abstract = "We determined redox-induced (im)mobilization of geogenic nickel (Ni) as well as binding forms of Ni in a Fluvisol at the River Velika Morava valley (Serbia), enriched with serpentine minerals. The selected site is representative for intensive agricultural land use in the area and susceptible to dynamic redox conditions due to periodical flooding. A seven-step sequential extraction, grain-size and light-liquid separation as well as mineralogical analyses were used, first, to assess binding forms of Ni and second, to determine relationships between grain-size fractions, abundance of heavy density minerals, and Ni concentration in the bulk soil. The sequential extraction revealed that the majority of Ni was in the residual fraction, followed by organic matter and Fe oxides. Fine grain-size fraction ( lt 63 mu m) was the major location of accumulation of Ni in the soil. Minerals which are characteristic for serpentine soils such as serpentine, spinels, hematite, and magnetite were found in silt and in the heavy density fraction (>2.9 g ml(-1)) of the medium and fine sand. However, the light minerals quartz, chlorite, micas, and secondary clay minerals dominate the soil mineral composition. Thus, total Ni concentration in the soil is derived from the content of Ni-bearing minerals and diluted by the minerals which are low in Ni. We simulated flooding using an automated biogeochemical microcosm system and determined the release dynamics of Ni at controlled redox potentials (E-H) in soil slurries. Pre-defined redox-windows were systematically created in steps of approximately 100 mV from reducing to oxidizing conditions while E-H and pH were continuously monitored. In parallel, the release dynamics of soluble nickel (Ni), iron (Fe), magnesium (Mg), manganese (Mn), dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), and sulfate (SO42-) were measured at each E-H-window. Our results highlighted that geogenic Ni can be mobilized to a considerable amount during low E-H, while elevating E-H from reducing to oxidizing conditions generated an immobilization Ni. We suggested that mobilization of Ni has been primarily affected by formation of Ni DOC complexes at low E-H, whereas Ni seems to be immobilized as a result of formation of Fe/Mn (hydro)oxides and the linked co-precipitation of Ni during oxidation. Factor analysis (FA) as multivariate statistical method explained 85.08% of the variance (67.89% and 17.19% component Nos. 1 and 2, respectively). The FA reveals that soluble Ni, Fe, DOC, Mn, and Mg were clustered in one group which indicate that the combined effect of DOC together with the chemistry of Fe, Mn, and Mg might be linked to the redox-induced release dynamics of Ni. The practical perspective of the study was to draw attention to dynamics of soluble Ni in fluctuating conditions for a better ecological risk assessment of floodplain sites under agricultural use. Nevertheless, similar studies should be conducted with further serpentine soils from various sites world-wide to verify the detected dynamics and processes.",
publisher = "Elsevier, Amsterdam",
journal = "Geoderma",
title = "Nickel in a serpentine-enriched Fluvisol: Redox affected dynamics and binding forms",
pages = "214-203",
volume = "263",
doi = "10.1016/j.geoderma.2015.09.004"
}

Rinklebe, J., Antić-Mladenović, S., Frohne, T., Staerk, H., Tomić, Z.,& Ličina, V.. (2016). Nickel in a serpentine-enriched Fluvisol: Redox affected dynamics and binding forms. in Geoderma
Elsevier, Amsterdam., 263, 203-214.
https://doi.org/10.1016/j.geoderma.2015.09.004

Rinklebe J, Antić-Mladenović S, Frohne T, Staerk H, Tomić Z, Ličina V. Nickel in a serpentine-enriched Fluvisol: Redox affected dynamics and binding forms. in Geoderma. 2016;263:203-214.
doi:10.1016/j.geoderma.2015.09.004 .

Rinklebe, Joerg, Antić-Mladenović, Svetlana, Frohne, Tina, Staerk, Hans-Joachim, Tomić, Zorica, Ličina, Vlado, "Nickel in a serpentine-enriched Fluvisol: Redox affected dynamics and binding forms" in Geoderma, 263 (2016):203-214,
https://doi.org/10.1016/j.geoderma.2015.09.004 . .

TY  - JOUR
AU  - Antić-Mladenović, Svetlana
AU  - Kresović, Mirjana
AU  - Rinklebe, Joerg
AU  - Frohne, Tina
AU  - Stärk, Hans-Joachim
AU  - Ličina, Vlado
PY  - 2015
UR  - http://aspace.agrif.bg.ac.rs/handle/123456789/3894
AB  - Thallium (Tl) is a highly toxic element, even in small concentrations, to a range of organisms and in different environments. Therefore, our aim was to study (i) Tl geochemical fractionation by the means of the modified BCR sequential extraction procedure and (ii) the impact of redox potential (EH) alteration and principal factors such as iron (Fe), manganese (Mn), dissolved organic carbon (DOC), chlorides (Cl) and sulfates (SO4 2) on Tl (im)mobilization in periodically flooded arable soil (Serbia). Flooding was simulated using an automated biogeochemical microcosm system that allows systematical control of pre-defined redox-windows. Afterwards, EH was increased stepwise for approximately 100 mV from reducing (-205 mV) to oxidizing (530 mV) conditions. EH was automatically monitored at 10 minutes intervals. Total duration of the experiment was 914 hours. The sequential extraction revealed majority of pseudo-total soil Tl (0.15 mg kg-1 ) in the residual fraction (85.5 %), following by reducible (10.2 %), oxidable (3.8 %) and acid soluble (exchangeable) (0.5 %) fraction. The soluble Tl concentrations (0.024-0.116 μg l-1 ) were significantly affected by EH, having an increase with EH increase (r=0.75, p lt 0.01, n=30). Concentrations of soluble Fe, Mn, and Doc showed significant negative correlations with soluble Tl (r=-0.78, r=-0.73 and r=-0.91, respectively, p lt 0.01, n=30), whereas Tl correlated significant positive with SO42and Cl(r=0.89, r=0.81, respectively, p lt 0.01, n=30). Thallium mobilization was attributed to several simultaneous processes, involving the reductive dissolution of Fe-Mn oxides and gradual oxidation of Tl-bearing metallic sulfides. Our results imply that soluble Tl concentrations might increase when soil redox status evolves from reducing to oxidizing conditions. Due to high Tl toxicity at low doses, and increasing flooding events, our findings suggest that Tl should be included in future monitoring of plants and groundwater on the site or on similar sites.
AB  - Talijum je veoma toksičan element i u niskim koncentracijama za razne organizme u okviru različitih delova životne sredine. Cilj rada bio je da se ispita (i) sadržaj talijuma u hemijskim frakcijama u zemljištu po modifikovanoj BCR proceduri i (ii) uticaj redoks potencijala (EH) i glavnih faktora, kao što su gvožđe (Fe), mangan (Mn), rastvorljiv organski ugljenik (DOC), hloridi (Cl -) i sulfati (SO4 2-) na (i)mobilizaciju talijuma u povremeno plavljenom obradivom zemljište (Srbija). Plavljenje zemljište je simulirano u laboratorijskim uslovima, uz korišćenje automatskog biogeohemijskog zatvorenog sistema koji dozvoljava sistematsku kontrolu definisanih redoks uslova. Nakon toga, redoks potencijal zemljište je postepeno povećavan u okvirima od po 100 mV od redukcionih (-205 mV) do oksidacionih (530 mV) uslova. Redoks potencijal je automatski meren u intervalima od 10 minuta. Ukupno vreme trajanja ogleda je bilo 914 sati. Hemijska frakcionacija je pokazala da se najveći deo ukupnog talijuma (0,15 mg kg -1) nalazi u rezidualnoj frakciji (85,5 %), a zatim u redukujućoj (10,2 %), oksidujućoj (3,8 %) i frakciji izmenljivo adsorbovanih elemenata (0,5 %). Redoks potencijal je značajno uticao na sadržaj rastvorljivog talijuma (0.024-0.116 μg l -1), koji se povećavao sa njegovim povećanjem (r=0.75, p lt 0.01, n=30). Rastvorljivi sadržaji Fe, Mn, i Doc su pokazali značajnu negativnu korelaciju sa rastvorljivim sadržajem Tl (r=-0.78, r=-0.73 i r=-0.91, redom, p lt 0.01, n=30), dok su utvržene značajne pozitivne korelacije između Tl i sulfata i hlorida (r=0.89, r=0.81, p lt 0.01, n=30). Mobilizacija talijuma može se dovesti u vezu sa nekoliko procesa koji se istovremeno odvijaju, a to su, između ostalih, rastvaranje Fe-i Mn-oksida u oksidacionim uslovima i postepena oksidacija metalnih sulfida koji sadrže Tl. Naša istraživanja ukazuju da sadržaji rastvorljivog Tl mogu da se povećavaju u kada se redoks potencijal menja od redukcionih ka oksidacionim uslovima. Naša istraživanja upućuju na neophodnost sistematskog praćenja sadržaja Tl u biljkama i podzemnim vodama, s obzirom na njegovu visoku toksičnost u niskim dozama, kao i učestalu pojavu plavljenja obradivih zemljišta.
PB  - Unija bioloških naučnih društava Jugoslavije, Beograd
T2  - Zemljište i biljka
T1  - Impact of different redox conditions on thallium (im)mobilization in soil (Serbia)
T1  - Uticaj različitih redoks uslova na (i)mobilizaciju talijuma u zemljište (Srbija)
EP  - 41
IS  - 2
SP  - 27
VL  - 64
UR  - https://hdl.handle.net/21.15107/rcub_agrospace_3894
ER  - 

@article{
author = "Antić-Mladenović, Svetlana and Kresović, Mirjana and Rinklebe, Joerg and Frohne, Tina and Stärk, Hans-Joachim and Ličina, Vlado",
year = "2015",
abstract = "Thallium (Tl) is a highly toxic element, even in small concentrations, to a range of organisms and in different environments. Therefore, our aim was to study (i) Tl geochemical fractionation by the means of the modified BCR sequential extraction procedure and (ii) the impact of redox potential (EH) alteration and principal factors such as iron (Fe), manganese (Mn), dissolved organic carbon (DOC), chlorides (Cl) and sulfates (SO4 2) on Tl (im)mobilization in periodically flooded arable soil (Serbia). Flooding was simulated using an automated biogeochemical microcosm system that allows systematical control of pre-defined redox-windows. Afterwards, EH was increased stepwise for approximately 100 mV from reducing (-205 mV) to oxidizing (530 mV) conditions. EH was automatically monitored at 10 minutes intervals. Total duration of the experiment was 914 hours. The sequential extraction revealed majority of pseudo-total soil Tl (0.15 mg kg-1 ) in the residual fraction (85.5 %), following by reducible (10.2 %), oxidable (3.8 %) and acid soluble (exchangeable) (0.5 %) fraction. The soluble Tl concentrations (0.024-0.116 μg l-1 ) were significantly affected by EH, having an increase with EH increase (r=0.75, p lt 0.01, n=30). Concentrations of soluble Fe, Mn, and Doc showed significant negative correlations with soluble Tl (r=-0.78, r=-0.73 and r=-0.91, respectively, p lt 0.01, n=30), whereas Tl correlated significant positive with SO42and Cl(r=0.89, r=0.81, respectively, p lt 0.01, n=30). Thallium mobilization was attributed to several simultaneous processes, involving the reductive dissolution of Fe-Mn oxides and gradual oxidation of Tl-bearing metallic sulfides. Our results imply that soluble Tl concentrations might increase when soil redox status evolves from reducing to oxidizing conditions. Due to high Tl toxicity at low doses, and increasing flooding events, our findings suggest that Tl should be included in future monitoring of plants and groundwater on the site or on similar sites., Talijum je veoma toksičan element i u niskim koncentracijama za razne organizme u okviru različitih delova životne sredine. Cilj rada bio je da se ispita (i) sadržaj talijuma u hemijskim frakcijama u zemljištu po modifikovanoj BCR proceduri i (ii) uticaj redoks potencijala (EH) i glavnih faktora, kao što su gvožđe (Fe), mangan (Mn), rastvorljiv organski ugljenik (DOC), hloridi (Cl -) i sulfati (SO4 2-) na (i)mobilizaciju talijuma u povremeno plavljenom obradivom zemljište (Srbija). Plavljenje zemljište je simulirano u laboratorijskim uslovima, uz korišćenje automatskog biogeohemijskog zatvorenog sistema koji dozvoljava sistematsku kontrolu definisanih redoks uslova. Nakon toga, redoks potencijal zemljište je postepeno povećavan u okvirima od po 100 mV od redukcionih (-205 mV) do oksidacionih (530 mV) uslova. Redoks potencijal je automatski meren u intervalima od 10 minuta. Ukupno vreme trajanja ogleda je bilo 914 sati. Hemijska frakcionacija je pokazala da se najveći deo ukupnog talijuma (0,15 mg kg -1) nalazi u rezidualnoj frakciji (85,5 %), a zatim u redukujućoj (10,2 %), oksidujućoj (3,8 %) i frakciji izmenljivo adsorbovanih elemenata (0,5 %). Redoks potencijal je značajno uticao na sadržaj rastvorljivog talijuma (0.024-0.116 μg l -1), koji se povećavao sa njegovim povećanjem (r=0.75, p lt 0.01, n=30). Rastvorljivi sadržaji Fe, Mn, i Doc su pokazali značajnu negativnu korelaciju sa rastvorljivim sadržajem Tl (r=-0.78, r=-0.73 i r=-0.91, redom, p lt 0.01, n=30), dok su utvržene značajne pozitivne korelacije između Tl i sulfata i hlorida (r=0.89, r=0.81, p lt 0.01, n=30). Mobilizacija talijuma može se dovesti u vezu sa nekoliko procesa koji se istovremeno odvijaju, a to su, između ostalih, rastvaranje Fe-i Mn-oksida u oksidacionim uslovima i postepena oksidacija metalnih sulfida koji sadrže Tl. Naša istraživanja ukazuju da sadržaji rastvorljivog Tl mogu da se povećavaju u kada se redoks potencijal menja od redukcionih ka oksidacionim uslovima. Naša istraživanja upućuju na neophodnost sistematskog praćenja sadržaja Tl u biljkama i podzemnim vodama, s obzirom na njegovu visoku toksičnost u niskim dozama, kao i učestalu pojavu plavljenja obradivih zemljišta.",
publisher = "Unija bioloških naučnih društava Jugoslavije, Beograd",
journal = "Zemljište i biljka",
title = "Impact of different redox conditions on thallium (im)mobilization in soil (Serbia), Uticaj različitih redoks uslova na (i)mobilizaciju talijuma u zemljište (Srbija)",
pages = "41-27",
number = "2",
volume = "64",
url = "https://hdl.handle.net/21.15107/rcub_agrospace_3894"
}

Antić-Mladenović, S., Kresović, M., Rinklebe, J., Frohne, T., Stärk, H.,& Ličina, V.. (2015). Impact of different redox conditions on thallium (im)mobilization in soil (Serbia). in Zemljište i biljka
Unija bioloških naučnih društava Jugoslavije, Beograd., 64(2), 27-41.
https://hdl.handle.net/21.15107/rcub_agrospace_3894

Antić-Mladenović S, Kresović M, Rinklebe J, Frohne T, Stärk H, Ličina V. Impact of different redox conditions on thallium (im)mobilization in soil (Serbia). in Zemljište i biljka. 2015;64(2):27-41.
https://hdl.handle.net/21.15107/rcub_agrospace_3894 .

Antić-Mladenović, Svetlana, Kresović, Mirjana, Rinklebe, Joerg, Frohne, Tina, Stärk, Hans-Joachim, Ličina, Vlado, "Impact of different redox conditions on thallium (im)mobilization in soil (Serbia)" in Zemljište i biljka, 64, no. 2 (2015):27-41,
https://hdl.handle.net/21.15107/rcub_agrospace_3894 .

TY  - JOUR
AU  - Antić-Mladenović, Svetlana
AU  - Rinklebe, Joerg
AU  - Frohne, Tina
AU  - Staerk, Hans-Joachim
AU  - Wennrich, Rainer
AU  - Tomić, Zorica
AU  - Ličina, Vlado
PY  - 2011
UR  - http://aspace.agrif.bg.ac.rs/handle/123456789/2726
AB  - Serpentine soils exist in many regions around the world; they are naturally enriched with nickel (Ni). An adequate understanding of soil processes determining Ni solubility is a special need particularly since less research has been addressed to Ni behavior under dynamic and controlled redox conditions. Our aim was (1) to characterize the properties of a serpentine soil and (2) to determine the impact of predefined redox windows on the mobility and dynamics of Ni in a serpentine soil. A soil with high geogenic Ni concentrations from Serbia was incubated using an automated biogeochemical microcosm system. Redox windows were created from reducing to oxidizing conditions in predefined steps of approximately 100 mV. Three microcosms were used as replicates; redox potential (E-H) and pH were automatically monitored every 10 min. The samples were centrifuged, and the supernatants were immediately filtered under N-2 atmosphere and analyzed for soluble Ni, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), and sulfate (SO (4) (2-) ). X-ray diffraction was performed to assess mineral composition of the soil grain-size fractions. Nickel binding forms in the bulk soil were determined by the sequential extraction according to Tessier et al. (1979). Total Ni concentration in the bulk soil was 550 mg kg(-1). Quartz, chlorite, serpentine minerals, and secondary minerals were the prevalent minerals. The residual fraction contained the most Ni (91.3%). Nickel percentages of the fractions: Fe/Mn oxides, organic matter, carbonate, and exchangeable were low. Soluble Ni concentrations varied in the range 77-166 mu g L-1, showing a linear decrease with increasing E-H. Soluble Ni was positive correlated with Fe, Mn, and DOC and inversely correlated with SO (4) (2-) . Dissolution and precipitation of Fe/Mn oxides, organic matter transformations, and adsorption on solids are important processes controlling the Ni solubility during redox change. Nickel concentrations at definite redox windows were in the same order of magnitude as the exchangeable Ni determined by the sequential extraction procedure. Our study demonstrates that considerable amounts of Ni can be mobilized during low E-H despite a high Ni retention capacity of the soil. The sequential extraction might provide a reliable estimation of the potential mobile Ni under dynamic redox alterations. The interactions of DOC, pH, Fe, and Mn (hydr)oxides are controlling the dynamics of soluble Ni under changing E-H conditions. It is important to verify the detected dynamics at various scales and in other serpentine soils in the future.
PB  - Springer Heidelberg, Heidelberg
T2  - Journal of Soils and Sediments
T1  - Impact of controlled redox conditions on nickel in a serpentine soil
EP  - 415
IS  - 3
SP  - 406
VL  - 11
DO  - 10.1007/s11368-010-0325-0
ER  - 

@article{
author = "Antić-Mladenović, Svetlana and Rinklebe, Joerg and Frohne, Tina and Staerk, Hans-Joachim and Wennrich, Rainer and Tomić, Zorica and Ličina, Vlado",
year = "2011",
abstract = "Serpentine soils exist in many regions around the world; they are naturally enriched with nickel (Ni). An adequate understanding of soil processes determining Ni solubility is a special need particularly since less research has been addressed to Ni behavior under dynamic and controlled redox conditions. Our aim was (1) to characterize the properties of a serpentine soil and (2) to determine the impact of predefined redox windows on the mobility and dynamics of Ni in a serpentine soil. A soil with high geogenic Ni concentrations from Serbia was incubated using an automated biogeochemical microcosm system. Redox windows were created from reducing to oxidizing conditions in predefined steps of approximately 100 mV. Three microcosms were used as replicates; redox potential (E-H) and pH were automatically monitored every 10 min. The samples were centrifuged, and the supernatants were immediately filtered under N-2 atmosphere and analyzed for soluble Ni, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), and sulfate (SO (4) (2-) ). X-ray diffraction was performed to assess mineral composition of the soil grain-size fractions. Nickel binding forms in the bulk soil were determined by the sequential extraction according to Tessier et al. (1979). Total Ni concentration in the bulk soil was 550 mg kg(-1). Quartz, chlorite, serpentine minerals, and secondary minerals were the prevalent minerals. The residual fraction contained the most Ni (91.3%). Nickel percentages of the fractions: Fe/Mn oxides, organic matter, carbonate, and exchangeable were low. Soluble Ni concentrations varied in the range 77-166 mu g L-1, showing a linear decrease with increasing E-H. Soluble Ni was positive correlated with Fe, Mn, and DOC and inversely correlated with SO (4) (2-) . Dissolution and precipitation of Fe/Mn oxides, organic matter transformations, and adsorption on solids are important processes controlling the Ni solubility during redox change. Nickel concentrations at definite redox windows were in the same order of magnitude as the exchangeable Ni determined by the sequential extraction procedure. Our study demonstrates that considerable amounts of Ni can be mobilized during low E-H despite a high Ni retention capacity of the soil. The sequential extraction might provide a reliable estimation of the potential mobile Ni under dynamic redox alterations. The interactions of DOC, pH, Fe, and Mn (hydr)oxides are controlling the dynamics of soluble Ni under changing E-H conditions. It is important to verify the detected dynamics at various scales and in other serpentine soils in the future.",
publisher = "Springer Heidelberg, Heidelberg",
journal = "Journal of Soils and Sediments",
title = "Impact of controlled redox conditions on nickel in a serpentine soil",
pages = "415-406",
number = "3",
volume = "11",
doi = "10.1007/s11368-010-0325-0"
}

Antić-Mladenović, S., Rinklebe, J., Frohne, T., Staerk, H., Wennrich, R., Tomić, Z.,& Ličina, V.. (2011). Impact of controlled redox conditions on nickel in a serpentine soil. in Journal of Soils and Sediments
Springer Heidelberg, Heidelberg., 11(3), 406-415.
https://doi.org/10.1007/s11368-010-0325-0

Antić-Mladenović S, Rinklebe J, Frohne T, Staerk H, Wennrich R, Tomić Z, Ličina V. Impact of controlled redox conditions on nickel in a serpentine soil. in Journal of Soils and Sediments. 2011;11(3):406-415.
doi:10.1007/s11368-010-0325-0 .

Antić-Mladenović, Svetlana, Rinklebe, Joerg, Frohne, Tina, Staerk, Hans-Joachim, Wennrich, Rainer, Tomić, Zorica, Ličina, Vlado, "Impact of controlled redox conditions on nickel in a serpentine soil" in Journal of Soils and Sediments, 11, no. 3 (2011):406-415,
https://doi.org/10.1007/s11368-010-0325-0 . .