Redox-induced mobilization of copper, selenium, and zinc in deltaic soils originating from Mississippi (U.S.A.) and Nile (Egypt) River Deltas: A better understanding of biogeochemical processes for safe environmental management.

Studies about the mobilization of potentially toxic elements (PTEs) in deltaic soils can be challenging, provide critical information on assessing the potential risk and fate of these elements and for sustainable management of these soils. The impact of redox potential (EH), pH, iron (Fe), manganese (Mn), sulfate (SO42-), chloride (Cl-), aliphatic dissolved organic carbon (DOC), and aromatic dissolved organic carbon (DAC) on the mobilization of copper (Cu), selenium (Se), and zinc (Zn) was studied in two soils collected from the Nile and Mississippi Rivers deltaic plains focused on increasing our understanding of the fate of these toxic elements. Soils were exposed to a range of redox conditions stepwise from reducing to oxidizing soil conditions using an automated biogeochemical microcosm apparatus. Concentrations of DOC and Fe were high under reducing conditions as compared to oxidizing conditions in both soils. The proportion of DAC in relation to DOC in solution (aromaticity) was high in the Nile Delta soil (NDS) and low in the Mississippi Delta soil (MDS) under oxidizing conditions. Mobilization of Cu was low under reducing conditions in both soils which was likely caused by sulfide precipitation and as a result of reduction of Cu2+ to Cu1+. Mobilization of Se was high under low EH in both soils. Release of Se was positively correlated with DOC, Fe, Mn, and SO42- in the NDS, and with Fe in the MDS. Mobilization of Zn showed negative correlations with EH and pH in the NDS while these correlations were non-significant in the MDS. The release dynamics of dissolved Zn could be governed mainly by the chemistry of Fe and Mn in the NDS and by the chemistry of Mn in the MDS. Our findings suggest that a release of Se and Zn occurs under anaerobic conditions, while aerobic conditions favor the release of Cu in both soils. In conclusion, the release of Cu, Se, and Zn under different reducing and oxidizing conditions in deltaic wetland soils should be taken into account due to increased mobilization and the potential environmental risks associated with food security in utilizing these soils for flooded agricultural and fisheries systems.

Bioavailability and risk assessment of potentially toxic elements in garden edible vegetables and soils around a highly contaminated former mining area in Germany.

Although soil contamination by potentially toxic elements (PTEs) in Europe has a history of many centuries, related problems are often considered as having been dealt with due to the enforcement of tight legislations. However, there are many unsolved issues. We aimed to assess PTE levels in highly contaminated soils and in garden edible vegetables using human health risk indices in order to evaluate the availability and mobilization of arsenic (As), copper (Cu), manganese (Mn), mercury (Hg), lead (Pb), and zinc (Zn). In four gardens in Germany, situated on, or in the vicinity of, a mine dump area, we planted beans (Phaseolus vulgaris ssp. nanus), carrots (Daucus sativus) and lettuce (Lactuca sativa ssp. capitata). We examined soil-to-plant mobilization of elements using transfer coefficient (TC), as well as soil contamination using contamination factor (CF), enrichment factor (EF), and bioaccumulation index (Igeo). In addition, we tested two human health risk assessment indices: Soil-induced hazard quotient (HQS) (representing the "direct soil ingestion" pathway), and vegetable-induced hazard quotient (HQV) (representing the "vegetable intake" pathway). The studied elements were highly elevated in the soils. The values in garden 2 were especially high (e.g., Pb: 13789.0 and Hg: 36.8 mg kg-1) and largely exceeded the reported regulation limits of 50 (for As), 40 (Cu), 400 (Pb), 150 (Zn), and 5 (Hg) mg kg-1. Similarly, element concentrations were very high in the grown vegetables. The indices of CF, EF and Igeo were enhanced even to levels that are rarely reported in the literature. Specifically, garden 2 indicated severe contamination due to multi-element deposition. The contribution of each PTE to the total of measured HQS revealed that Pb was the single most important element causing health risk (contributing up to 77% to total HQS). Lead also posed the highest risk concerning vegetable consumption, contributing up to 77% to total HQV. The presence of lead in both cases was followed by that of As, Mn and Hg. We conclude that in multi-element contamination cases, along with high-toxicity elements (here, Pb, As and Hg) other elements may also be responsible for increasing human health risks (i.e., Mn), due to the possibility of adverse synergism of the PTEs.

Biogeochemistry of Ni and Pb in a periodically flooded arable soil: Fractionation and redox-induced (im)mobilization.

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 (EH) 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 µg l-1 while Pb ranged from 3.0 to 21.4 µg l-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.

Redox-controlled release dynamics of thallium in periodically flooded arable soil.

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 µg L-1) increased significantly with increases in EH (r = 0.80, p < 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, Tl 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.

Amendment of biochar reduces the release of toxic elements under dynamic redox conditions in a contaminated floodplain soil.

Biochar (BC) can be used to remediate soils contaminated with potential toxic elements (PTEs). However, the efficiency of BC to immobilize PTEs in highly contaminated floodplain soils under dynamic redox conditions has not been studied up to date. Thus, we have (i) quantified the impact of pre-definite redox conditions on the release dynamics of dissolved aluminum (Al), arsenic (As), cadmium (Cd), copper (Cu), nickel (Ni), and zinc (Zn) in a highly contaminated soil (CS) (non-treated) and in the same soil treated with 10 g kg(-1) biochar based material (CS+BC), and (ii) assessed the efficacy of the material to reduce the concentrations of PTEs in soil solution under dynamic redox conditions using an automated biogeochemical microcosm apparatus. The impact of redox potential (EH), pH, dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), iron (Fe), manganese (Mn), and sulfate (SO4(2-)) on dynamics of PTEs was also determined. The EH was lowered to +68 mV and afterwards increased stepwise to +535 mV. Significant negative correlation between EH and pH in CS and CS+BC was detected. The systematic increase of EH along with decrease of pH favors the mobilization of PTEs in CS and CS+BC. The material addition seems to have little effect on redox processes because pattern of EH/pH and release dynamics of PTEs was basically similar in CS and CS+BC. However, concentrations of dissolved PTEs were considerably lower in CS+BC than in CS which demonstrates that BC is able to decrease concentrations of dissolved PTEs even under dynamic redox conditions.

Redox effects on release kinetics of arsenic, cadmium, cobalt, and vanadium in Wax Lake Deltaic freshwater marsh soils.

The impact of redox potential (EH), pH, iron (Fe), manganese (Mn), chloride (Cl(-)), aliphatic and aromatic dissolved organic carbon (DOC), and sulfate ( [Formula: see text] ) on the release of dissolved arsenic (As), cadmium (Cd), cobalt (Co), and vanadium (V) were studied in Louisiana freshwater marsh Wax Lake Delta soil (Mississippi River) using an automated biogeochemical microcosm apparatus. The experiment was conducted from reducing (-60 mV) to stepwise oxidizing (+491 mV) conditions. The initial pH was 7.4 and decreased under reducing conditions to 4.9, and remained constant during the increase of EH. Concentrations of As (1.3-120.5 µg L(-1)), V (0.9-48.6 µg L(-1)), Fe, DOC, and the specific UV absorbance increased under reducing conditions and decreased with rising EH. Release of As and V appeared to be related to changes of EH/pH, co-precipitation with Fe oxides, and the release of dissolved aromatic carbon compounds. Concentrations of soluble Cd (4.8-11.2 µg L(-1)), Mn, [Formula: see text] , and Cl(-) increased under oxidizing conditions. Release of Co (166.6-258.2 µg L(-1)) was related to the chemistry of Fe, Mn and DOC. Phospholipid fatty acids analysis indicated the potential for the microbial community to be involved in biogeochemical processes such as the formation of sulfides, oxidation and reduction of compounds, and the bio-methylation of elements such as As. Overall, we measured a release of As and V under anoxic conditions, while oxic conditions favored the release of Cd. These results outline concern on the potential risk of mobilization of toxic elements in temporary waterlogged soils for agricultural purposes in deltaic ecosystems.