Antagonistic Cd and Zn isotope behavior in the extracted soil fractions from industrial areas.

The remobilization of metals accumulated in contaminated soils poses a threat to humans and ecosystems in general. Tracing metal fractionation provides valuable information for understanding the remobilization processes in smelting areas. Based on the difference between the isotopic system of Cd and Zn, this work aimed to couple isotope data and their leachability to identify possible remobilization processes in several soil types and land uses. For soil samples, the δ66/64Zn values ranged from 0.12 ± 0.05‰ to 0.28 ± 0.05‰ in Avilés (Spain) and from - 0.09 ± 0.05‰ to - 0.21 ± 0.05‰ in Príbram (Czech Republic), and the δ114/110Cd ranged from - 0.13 ± 0.05‰ to 0.01 ± 0.04‰ in Avilés and from - 0.86 ± 0.27‰ to - 0.24 ± 0.05‰ in Príbram. The metal fractions extracted using chemical extractions were always enriched in heavier Cd isotopes whilst Zn isotope systematics exhibited light or heavy enrichment according to the soil type and land uses. Coupling Zn and Cd systematics provided a tool for deciphering the mechanisms behind the remobilization processes: leaching of the anthropogenic materials and/or metal redistribution within the soil components prior to remobilization.

Multiple pollution sources unravelled by environmental forensics techniques and multivariate statistics.

Industrial sites affected by anthropogenic contamination, both past and present-day, commonly have intricate pollutant patterns, and source discrimination can be thus highly challenging. To this goal, this paper presents a novel approach combining multivariate statistics and environmental forensic techniques. The efficiency of this methodology was exemplified in a severely polluted estuarine area (Avilés, Spain), where factor analysis and clustering were performed to identify sub-areas with distinct geochemical behaviour. Once six clusters were defined and a pollution index applied, forensic tools revealed that the As speciation, Pb isotopes, and PAHs molecular ratios were useful to categorise the cluster groups on the basis of distinct pollution sources: Zn-smelting, coaly particles and waste disposal. Overall, this methodology offers valuable insight into pollution sources identification, which can be extended to comparable scenarios of complexly polluted environmental compartments. The information gathered using this approach is also important for the planning of risk assessment procedures and potential remediation strategies.

Cerium anomalies in riverbanks: Highlight into the role of ferric deposits.

In wetlands, stream riverbanks represent a large redox reactive front. At their surface, ferric deposits promote their capacity to trap nutrients and metals. Given that rare earth elements (REE) are now considered as emerging pollutants, it seems that the riverbank interface is a strategic area between wetlands and streams in terms of controlling the environmental dissemination of REE. Therefore, the evolutions of the REE distribution and cerium (Ce) anomaly (Ce/Ce*, i.e. depleted or enriched Ce concentration compared to the other REE) were studied at various locations on a riverbank. The positive Ce anomaly is related to a high Fe content, a low organic carbon/iron ratio ((OC)/Fe) and newly formed Fe oxyhydroxides independently of their interactions with organic matter. Micro-X ray fluorescence (µ-XRF) mapping confirms Ce accumulation with ferric deposits. The Ce speciation exhibits a mix of Ce(III) and Ce(IV) in the ferric deposits, almost 20% of Ce occurred as Ce(IV) due to oxidation by newly formed Fe oxyhydroxides, while the subsurface horizons only display Ce(III). These results provide evidence that the Ce anomaly variation observed in stream water between low and high flow periods is partly due to the erosion of ferric deposits exhibiting a positive Ce anomaly. Therefore, the Ce anomaly can be considered as a fingerprint of the release of Fe colloids in the rivers and streams connected to the wetland.

Iron speciation at the riverbank surface in wetland and potential impact on the mobility of trace metals.

Fe oxyhydroxides in riverbanks and their high binding capacity can be used to hypothesize that riverbanks may act as a "biogeochemical filter" between wetlands and rivers and may constitute a major mechanism in the trapping and flux regulation of chemical elements. Until now, the properties of Fe minerals have been very poorly described in riverbanks. The goals of the present work are to identify Fe speciation in riverbanks where ferric deposits are observed and to determine their impact on the metal behavior (As, Co, Cu, Ni, Pb, Zn, etc.). At the surface, Fe speciation is mainly composed of small poorly crystalline Fe phases, i.e. ferrihydrite (~30%), Fe-OM associations (~40%) as well as crystalline Fe phases, i.e. goethite (~35%). At the subsurface, the Fe distribution is dominated by goethite (~35%) and Fe-mica (~35%), the proportion of which increases at the expense of ferrihydrite and the Fe-OM associations. At the riverbank surface, ferrihydrite and the Fe-OM associations are therefore the main Fe hosting phases in response to (i) the fast Fe(II) oxidation induced by the presence of O2 and (ii) the high amount of OM favoring the formation of nano-phases bound to OM (Fe monomers, polymers and nanoparticles) and preventing mineralogical transformation (ferrihydrite into goethite). During the high-water level period (high flow), a strong erosion of the riverbank transfers these ferric deposits into the river. However, the physicochemical parameters of the river (pH 6.6-7.6 and continuous oxic conditions) do not promote the dissolution of Fe oxyhydroxides and OM. Ferric deposits and the associated trace metals are therefore maintained as colloids/particles and are exported to the outlet. All of the results presented here demonstrate that the ferric deposits trap metals on a seasonal basis and are therefore a key factor in the mobilization of metals during riverbank erosion by river flow.