Influence of oxic/anoxic condition on sorption behavior of PFOS in sediment

Sediment components and redox properties change with oxic/anoxic condition, which affect the environmental transport of perfluorooctane sulfonate (PFOS). Herein, the influence of oxic/anoxic condition on the variation of redox and residual components of sediments, where organic matter, iron and manganese oxides are separated from the original sediment collected from Lake Taihu, China, are investigated. Meanwhile, the distinguishing sorption behaviors of PFOS on various residual sediments under oxic and anoxic condition are studied. Sediment after extracting iron and manganese (S-FeMn), which possessed the highest organic carbon (0.99%), had the highest affinity for PFOS under oxic condition. However, anoxic environment resulted in an increase of the pH, dissolving of organic carbon and de-protonation of S-FeMn, which caused the lower sorption capacity of PFOS on S-FeMn. Sediment after extracting manganese (S-Mn) had the higher sorption ability in anoxic environment because the Fe2+ from S-Mn provided more effective electrostatic sites for anionic PFOS. When the environment changed to oxic condition, the iron existed as trivalent form in S-Mn, which resulted in a block of effective sorption site and reduced the sorption amounts of PFOS. The higher percentage of manganese oxides restrained the sorption of PFOS. Hence, whether or not oxic/anoxic condition promoted the PFOS sorption depended on both the percentage and form of various components in the sediment. The study generated further insight into the environmental transport of PFOS in the sediments with different properties and the wetland system, where oxic/anoxic subsurface flow was constructed

Iron speciation in natural organic matter colloids

International audienc

Mobilization of Zn upon waterlogging riparian Spodosols is related to reductive dissolution of Fe minerals

Contaminated riparian soils can release metals to surface water. Periodic waterlogging affects metal mobility but the processes and soil factors governing net trends are not well understood. Experiments were combined with geochemical modelling to identify processes explaining the dynamics of zinc (Zn) in contaminated soils following waterlogging. Samples were collected from 12 Spodosols near streams in a metal-contaminated area and four similar but uncontaminated soils were sampled in a reference area. Air-dried samples were submerged and incubated under N2. The soil redox potential decreased from 470 mV initially to approximately 30 mV over 2 months. The pore-water Zn concentrations surprisingly increased over the same period by, on average, a factor of 18 (range 0.6–80; immobilization in one soil only) despite an increase in pH of 1.8 units, on average. Dissolved organic matter (DOM) in the soil solution increased during waterlogging but the observed increase in Zn solubility could not be explained by increased complexation with DOM, because the estimated Zn2+ activity also increased by a factor of 18 on average (range 0.2–82). Speciation modelling suggests that Zn mobilization during waterlogging results from Fe2+ displacing sorbed Zn2+ from particulate organic matter and from dissolution of Zn-bearing Fe/Mn oxyhydroxides. This hypothesis is supported by the significant positive correlation (r = 0.87, n = 13) between the factor change in pore-water Zn concentration and the ratio of dithionite-extractable Fe to organic carbon content. These results show that Fe dynamics are important for predicting the fate of trace metals in anoxic soils.L. Van Laer, F. Degryse, K. Leynen and E. Smolder

Floodplain Effects On the Transport of Dissolved and Colloidal Trace Elements in the East Pearl River, Mississippi

Substantial work suggests that floodplain wetlands could play a role in modifying fluvial fluxes of dissolved and colloidal trace elements. Yet, few studies have directly addressed this issue. We examined trace elements in the East Pearl River (Mississippi or Louisiana, USA), which is surrounded by wetlands that are temporally more or less connected to the river depending on river stage. Dissolved and colloidal trace element samples, along with ancillary data, including dissolved organic carbon and nutrients, were collected during eight surveys of this system at different flow stages from November 2007 to September 2008. Hydrology of the system is complex due to seasonal changes in water sources as well as potential inputs from the floodplain wetlands and the hyporheic zone. We therefore considered effects including nonconservative mixing of water sources, saltwater intrusion, and floodplain wetland flux requirements needed to support observed downstream concentration changes. During moderately high discharge, fluxes of many elements (e.g., Cd, Fe, Mn, and Zn) increased downstream by 20% or more, with inputs from the floodplain wetlands as the apparent source. At the highest discharge, however, wetland inputs to the river may have been rate-limited (i.e., the wetland source was flushed faster than biogeochemical processes could regenerate dissolved or colloidal material). At low discharge, other effects, including saltwater intrusion and hyporheic zone interactions, are important. Both redox processes and organic ligands (or dissolved organic carbon), along with the supply of wetland inputs (or removal) relative to river fluxes, appear to be key factors determining floodplain wetland effects. While the behavior of some elements suggests they were dominantly affected by redox processes (Mn and V) or by organic complexation (dissolved Fe and light rare earths), other elements were affected by more than one process in ways that remain obscure (Cu). Overall our results are broadly consistent with previous field, laboratory, and modeling studies and suggest that a better understanding of the sources and transformations of Fe is a key area for future research

Dinâmica da mobilização de elementos em solos da Amazônia submetidos à inundação Dinamics of elements in soils from Amazonia after controlled inundation

Parte significativa de solos da Amazônia permanece saturada ou inundada por períodos que podem variar de alguns dias a vários meses, em decorrência de enchentes ou deficiência de drenagem em algumas áreas, resultando em alterações químicas, físicas e biológicas nos solos. Este trabalho foi conduzido com o objetivo de avaliar a dinâmica da mobilização de Al, Ca, Fe, K, Mg, Mn, Na, Si e P em solos da Amazônia submetidos a inundação. Amostras de vários solos foram submetidas à inundação durante seis meses. Alíquotas da solução foram coletadas periodicamente durante o tempo de inundação e determinaram-se os teores dos diversos elementos em solução. A inundação influenciou a cinética dos elementos, com aumento da mobilização dos mesmos, principalmente, nas primeiras semanas. Os teores de Fe em solução foram mais elevados para os solos mais ricos em Fe amorfo. Em amostras com baixos teores de Fe amorfo e baixo conteúdo de matéria orgânica, os teores de Fe em solução foram muito reduzidos. O teor de P em solução foi influenciado por todas as formas de P. O P ligado ao Fe foi a forma que maior influência exerceu sobre o teor de P solúvel. Os teores dos cátions Ca, Mg, K e Na, em solução, foram diretamente influenciados por seus respectivos teores trocáveis, bem como pela cinética do Fe e do Mn.<br>Significant part of Amazonia soils stays partially or completely waterlogged for varying periods of days to months, as result of widespread inundation or drainage deficiency in some areas, causing changes in chemical, physical and biological properties. In this work, we aimed to evaluate the dynamics of mobilization of Al, Ca, Fe, K, Mg, Mn, Na, Si, P in soils subjected to controlled six months inundation. Soil solution aliquots were collected periodically during the inundation period, determining all elements in solution. The inundation influenced the kinetics of elements, increasing their mobilization, notably in the first weeks. Levels of Fe in solution were higher in soils with greater amounts of amorphous Fe. In soils with low amorphous Fe and low organic matter contents, mobilization of Fe was very low. Levels of P in solution were influenced by all P forms, but Fe-P forms exerted the greatest influence on mobilized P. Levels of Ca, Mg, K and Na in solution were directly influenced by their exchangeable levels, as well by the Mn and Fe kinetics