In Situ Vivianite Formation in Intertidal Sediments: Ferrihydrite-Adsorbed P Triggers Vivianite Formation.

Coastal sediments are a key contributor to oceanic phosphorus (P) removal, impacting P bioavailability and primary productivity. Vivianite, an Fe(II)-phosphate mineral, can be a major P sink in nonsulfidic, reducing coastal sediments. Despite its importance, vivianite formation processes in sediments remain poorly understood.

Geochemical Decoupling of Iron and Zinc during Transformation of Zn-Bearing Ferrihydrite in Reducing Sediments.

The transformation of the mineral ferrihydrite in reducing environments, and its impact on the mobility of incorporated trace metals, has been investigated in model laboratory studies, but studies using complex soil or sediment matrices are lacking. Here, we studied the transformation of zinc (Zn)-bearing ferrihydrite labeled with Fe and mixed with natural sediments, incubated in reducing conditions for up to six months. We tracked the evolution of Fe and Zn speciation with Fe Mössbauer spectroscopy and with bulk and micro-X-ray absorption spectroscopy.

Emerging investigator series: Coprecipitation with glucuronic acid limits reductive dissolution and transformation of ferrihydrite in an anoxic soil.

Ferrihydrite, a poorly crystalline Fe(III)-oxyhydroxide, is abundant in soils and is often found associated with organic matter. Model studies consistently show that in the presence of aqueous Fe(II), organic carbon (OC)-associated ferrihydrite undergoes less transformation than OC-free ferrihydrite. Yet, these findings contrast microbial reductive dissolution studies in which the OC promotes the reductive dissolution of Fe(III) in ferrihydrite and leads to the release of associated OC.

Interactions between iron and carbon in permafrost thaw ponds.

Thawing permafrost forms "thaw ponds" that accumulate and transport organic carbon (OC), redox-active iron (Fe), and other elements. Although Fe has been shown to act as a control on the microbial degradation of OC in permafrost soils, the role of iron in carbon cycling in thaw ponds remains poorly understood. Here, we investigated Fe-OC interactions in thaw ponds in partially and fully thawed soils ("bog" and "fen" thaw ponds, respectively) in a permafrost peatland complex in Abisko, Sweden, using size separation (large particulate fraction (LPF), small particulate fraction (SPF), and dissolved fraction (DF)), acid extractions, scanning electron microscopy (SEM), Fe K-edge X-ray absorption spectroscopy (XAS), and Fourier Transform Infrared (FTIR) spectroscopy.

Iron Oxyhydroxide Transformation in a Flooded Rice Paddy Field and the Effect of Adsorbed Phosphate.

The mobility and bioavailability of phosphate in paddy soils are closely coupled to redox-driven Fe-mineral dynamics. However, the role of phosphate during Fe-mineral dissolution and transformations in soils remains unclear. Here, we investigated the transformations of ferrihydrite and lepidocrocite and the effects of phosphate pre-adsorbed to ferrihydrite during a 16-week field incubation in a flooded sandy rice paddy soil in Thailand.

Simultaneously decreasing arsenic and cadmium in rice by soil sulfate and limestone amendment under intermittent flooding.

Water management in paddy soils can effectively reduce the soil-to-rice grain transfer of either As or Cd, but not of both elements simultaneously due to the higher mobility of As under reducing and Cd under oxidizing soil conditions. Limestone amendment, the common form of liming, is well known for decreasing Cd accumulation in rice grown on acidic soils. Sulfate amendment was suggested to effectively decrease As accumulation in rice, especially under intermittent soil flooding.

Structural Effects of Aluminum and Iron Occupancy in Minerals of the Jarosite-Alunite Solid Solution.

The alunite supergroup of minerals contains several hydroxysulfate mineral phases that commonly occur in acidic natural and engineered environments. The main division of the mineral supergroup defines two minerals, jarosite and alunite, based on the relative structural occupancy by Al or Fe, respectively. However, intermediate members of the jarosite-alunite solid solution have not been extensively characterized, especially in the environment.

Temporal development of arsenic speciation and extractability in acidified and non-acidified paddy soil amended with silicon-rich fly ash and manganese- or zinc-oxides under flooded and drainage conditions.

Oxides of silicon (Si), manganese (Mn), and zinc (Zn) have been used as soil amendments to reduce As mobility and uptake in paddy soil systems. However, these amendments are hypothesized to be affected differently depending on the soil pH and their effect on As speciation in rice paddy systems is not fully understood. Herein, we used a microcosm experiment to investigate the effects of natural Si-rich fly ash and synthetic Mn and Zn oxides on the temporal development of porewater chemistry, including aqueous As speciation (As(III), As(V), MMA, DMA, and DMMTA) and solid-phase As solubility, in a naturally calcareous soil with or without soil acidification (with sulfuric acid) during 28 days of flooding and subsequent 14 days of drainage.

Geochemical Soil Atlas of Switzerland - Distribution of Toxic Elements.

Chemical elements such as copper and molybdenum are essential for animal and human health but may become toxic at elevated concentrations depending on the exposure and intake rate. Other elements such as mercury pose a threat to human health at already low concentrations. The soil acts as the main source of these elements for plant uptake and is thus driving accumulation along the food chain.

Contact with soil impacts ferrihydrite and lepidocrocite transformations during redox cycling in a paddy soil.

Iron (Fe) oxyhydroxides can be reductively dissolved or transformed under Fe reducing conditions, affecting mineral crystallinity and the sorption capacity for other elements. However, the pathways and rates at which these processes occur under natural soil conditions are still poorly understood. Here, we studied Fe oxyhydroxide transformations during reduction-oxidation cycles by incubating mesh bags containing ferrihydrite or lepidocrocite in paddy soil mesocosms for up to 12 weeks.

A New Approach for Investigating Iron Mineral Transformations in Soils and Sediments Using Fe-Labeled Minerals and Fe Mössbauer Spectroscopy.

Iron minerals in soils and sediments play important roles in many biogeochemical processes and therefore influence the cycling of major and trace elements and the fate of pollutants in the environment. However, the kinetics and pathways of Fe mineral recrystallization and transformation processes under environmentally relevant conditions are still elusive. Here, we present a novel approach enabling us to follow the transformations of Fe minerals added to soils or sediments in close spatial association with complex solid matrices including other minerals, organic matter, and microorganisms.

Decreasing arsenic in rice: Interactions of soil sulfate amendment and water management.

Accumulation of inorganic arsenic (iAs) and dimethylarsenate (DMA) in rice threatens human health and rice yield, respectively. We studied the yet unclear interactions of soil sulfate amendment and water management for decreasing As accumulation in rice grain in a pot experiment. We show that soil sulfate amendment (+200 mg S/kg soil) decreased grain iAs by 44% without clearly increasing grain DMA under intermittent flooding from booting stage to maturation.

Ferrihydrite transformations in flooded paddy soils: rates, pathways, and product spatial distributions.

Complex interactions between redox-driven element cycles in soils influence iron mineral transformation processes. The rates and pathways of iron mineral transformation processes have been studied intensely in model systems such as mixed suspensions, but transformation in complex heterogeneous porous media is not well understood. Here, mesh bags containing 0.

Coexisting Goethite Promotes Fe(II)-Catalyzed Transformation of Ferrihydrite to Goethite.

In redox-affected soil environments, electron transfer between aqueous Fe(II) and solid-phase Fe(III) catalyzes mineral transformation and recrystallization processes. While these processes have been studied extensively as independent systems, the coexistence of iron minerals is common in nature. Yet it remains unclear how coexisting goethite influences ferrihydrite transformation.

Stabilization of Ferrihydrite and Lepidocrocite by Silicate during Fe(II)-Catalyzed Mineral Transformation: Impact on Particle Morphology and Silicate Distribution.

Interactions between aqueous ferrous iron (Fe(II)) and secondary Fe oxyhydroxides catalyze mineral recrystallization and/or transformation processes in anoxic soils and sediments, where oxyanions, such as silicate, are abundant. However, the effect and the fate of silicate during Fe mineral recrystallization and transformation are not entirely understood and especially remain unclear for lepidocrocite. In this study, we reacted (Si-)ferrihydrite (Si/Fe = 0, 0.

Mineral characterization and composition of Fe-rich flocs from wetlands of Iceland: Implications for Fe, C and trace element export.

In freshwater wetlands, redox interfaces characterized by circumneutral pH, steep gradients in O, and a continual supply of Fe(II) form ecological niches favorable to microaerophilic iron(II) oxidizing bacteria (FeOB) and the formation of flocs; associations of (a)biotic mineral phases, microorganisms, and (microbially-derived) organic matter. On the volcanic island of Iceland, wetlands are replenished with Fe-rich surface-, ground- and springwater. Combined with extensive drainage of lowland wetlands, which forms artificial redox gradients, accumulations of bright orange (a)biotically-derived Fe-rich flocs are common features of Icelandic wetlands.

Two-year and multi-site field trials to evaluate soil amendments for controlling cadmium accumulation in rice grain.

Representing the staple crop for half of the world population, rice can accumulate high levels of cadmium (Cd) in its grain, posing concerns on food safety. Different soil amendments have been proposed to decrease Cd accumulation in rice grain by either decreasing soil Cd availability, introducing competitive ions on Cd uptake, or down-regulating the expression of transporters for Cd uptake. However, the effectiveness of soil amendments applied alone or in combinations needs to be tested under field conditions.

Arsenic redox transformations and cycling in the rhizosphere of and .

(PV) and (PQ) are reported to hyperaccumulate arsenic (As) when grown in Asrich soil. Yet, little is known about the impact of their unique As accumulation mechanisms on As transformations and cycling at the soil-root interface. Using a combined approach of two-dimensional (2D), sub-mm scale solute imaging of arsenite (As), arsenate (As), phosphorus (P), manganese (Mn), iron (Fe) and oxygen (O), we found localized patterns of As/As redox transformations in the PV rhizosphere (As/As ratio of 0.

Mercury Reduction by Nanoparticulate Vivianite.

Mercury (Hg) is a toxic trace element of global environmental concern which has been increasingly dispersed into the environment since the industrial revolution. In aquatic and terrestrial systems, Hg can be reduced to elemental Hg (Hg) and escape to the atmosphere or converted to methylmercury (MeHg), a potent neurotoxin that accumulates in food webs. Fe-bearing minerals such as magnetite, green rusts, siderite, and mackinawite are recognized Hg reducers.

The Voltaic Effect as a Novel Mechanism Controlling the Remobilization of Cadmium in Paddy Soils during Drainage.

Excessive cadmium (Cd) accumulation in rice grain is a global issue that affects human health. The drainage of paddy soils during the grain filling period leads to the remobilization of Cd in soils, resulting in most of the Cd accumulated in rice grain. The rate of Cd remobilization during drainage differs markedly among soils, but the mechanisms underlying these differences remain largely unknown.

The Effect of Aeration on Mn(II) Sorbed to Clay Minerals and Its Impact on Cd Retention.

Manganese is a redox-sensitive element in soils and sediments that plays an important role in the retention of trace elements. Under anoxic conditions, clay minerals were shown to increase Cd retention by favoring the precipitation of Mn(II) phases. In this study, we investigated the influence of aeration on anoxically formed Mn solid phases and its impact on Cd retention in the presence of two clay minerals with low Fe contents, a natural kaolinite (KGa-1b) and a synthetic montmorillonite (Syn-1).