Vivianite Formation Research Articles

Nano-magnetite enhances dissimilated iron reduction to vivianite from sewage by structuring an enormous and compact electron transfer network

Acting as both terminal and conductor of extracellular electron transfer (EET), little studies were focused on how nano-magnetite participated in the dissimilated iron reduction (DIR), especially the synthesis of vivianite, which was the typical DIR products from sewage. In this study, nano-magnetite was confirmed to enhance DIR of ferrihydrite and akaganeite for vivianite recovery from sewage. Nano-magnetite incorporation enriched Comamonas and Geobacter in sewage, and microbial protein content was increased by 123 % and 57 % in ferrihydrite and akaganeite batches, respectively. In Geobacter sulfurreducens PCA pure culture, vivianite yield was promoted by 21 % and 37 % in ferrihydrite and akaganeite batches in the presence of nano-magnetite, respectively. Due to its nanoscale size and superior electrical conductivity, nano-magnetite embedded in the gaps formed by the microorganisms and electron acceptor, and architected coherent conductive pathways to promote EET. Simultaneously, the addition of nano-magnetite stimulated the secretion of proteins, polysaccharides, and humic acids in the extracellular polymeric substances. Nano-magnetite addition structured an enormous and compact electron transfer network, thus enhanced DIR and vivianite formation. Our study proposed a new strategy to promote iron-reduction-coupled phosphorus recovery with natural DIR products, and provided theoretical support for clarifying the interaction between minerals and microorganisms.

A deep treatment process for chemical polishing wastewater towards resource recovery: Optimization and performance

The chemical polishing industry generates abundant wastewater that contains high concentrations of phosphoric acid and metal ions. In light of the rapid growth of the economy and the stringent demands for sustainability, developing cost-effective and energy-efficient technologies for wastewater treatment is crucial. Herein, an EPRC-ICT-ANT process integrating electrodialysis, iron contact, and alkali neutralization, was proposed to deeply treat chemical polishing wastewater and achieve optimal recovery of acid, phosphorus, and aluminum. The results indicated that with the electrochemical phosphoric acid recovery cell (EPRC), the maximum recovery efficiency and final phosphoric acid concentration were 34.6 % and 25.2 g/L. Following the iron contact tank and alkali neutralization tank (ICT-ANT) treatment, a remarkable 99.17 % removal of Al3+ and 49.5 kg/t wastewater yield of AlPO4 were achieved. Simultaneously, the released Fe2+ and remaining PO43- triggered the rapid formation of vivianite with a yield of 120.7 kg/t wastewater. This comprehensive treatment strategy led to the near-complete removal of Al3+ and PO43- (∼100 %) with an impressive recovery of Al3+ (∼100 %) and PO43- (75.7 %), emphasizing its immense potential for chemical polishing wastewater treatment.

The screening of iron oxides for long-term transformation into vivianite to recover phosphorus from sewage

The reducibility of iron oxides, depending on their properties, influences the kinetics of dissimilatory iron reduction (DIR) during vivianite recovery in sewage. This study elucidated the correlation between properties of iron oxides and kinetics of DIR during the long-term transformation into vivianite, mediated by Geobacter sulfurreducens PCA and sewage. The positive correlation between surface reactivity of iron oxides and reduction rate constant (k) influenced the terminal vivianite recovery efficiency. Akaganeite with the highest adhesion work and surface energy required the lowest reduction energy (Ea), obtained the highest k of 1.36 × 10–2 day-1 and vivianite recovery efficiency of 43 %. The vivianite yield with akaganeite as iron source was 76–164 % higher than goethite, hematite, feroxyhyte, and ferrihydrite in sewage. The distribution of P with akaganeite during DIR in sewage further suggested a more efficient pathway of direct vivianite formation via bio-reduced Fe(II) rather than indirect reduction of ferric phosphate precipitates. Thus, akaganeite was screened out as superior iron source among various iron oxides for vivianite recovery, which provided insights into the fate of iron sources and the cycle of P in sewage.

Hematite enhances microbial autotrophic nitrate removal in carbonate and phosphate-rich environments by increasing Fe(II) activity

Groundwater contamination by nitrates presents significant risks to both human health and the environment. In groundwater characterized as oligotrophic—low in organic carbon, but abundant in carbonate and phosphate—chemolithoautotrophic bacteria, including nitrate-reducing Fe(II)-oxidizing bacteria (NRFeOB), play a vital role in denitrification. The chemoautotrophic nitrate reduction is sensitive to environmental factors, including widespread iron oxides like hematite in nature. However, the specific mechanisms of this influence remain unclear. We examined the mechanism of how hematite impacts autotrophic nitrate reduction in a model NRFeOB community known as culture KS. We found that hematite enhances the rate of autotrophic nitrate reduction by promoting Fe(II) oxidation. Mössbauer spectroscopy detected a significant amount of adsorbed Fe(II) when hematite was present, leading to a reduction in dissolved ferrous iron. In conjunction with XRD data, it can be inferred that the formation of vivianite decreased, thereby increasing the Fe(II) activity in the reaction system. Within the culture KS bacterial consortium, hematite fosters the proliferation of autotrophic microorganisms, specifically Gallionellaceae, and amplifies the presence of denitrifying microbes, notably Rhodanobacter. This dual enhancement improves Fe(II) utilization and nitrate reduction capabilities. Our findings highlight intricate interactions between hematite and a model NRFeOB community, offering insights into groundwater nitrate removal mechanisms and the ecological strategies of autotrophic bacteria in mineral-rich environments.

Mechanistic insights into sulfadimethoxine degradation via microbially driven Fenton reactions

Biodegradation, while cost-effective, is hindered by the requirement for specialized microorganisms and co-contaminants. Innovative biological technologies like the microbially driven Fenton reaction, hold promise for enhancing degradation efficiency. However, the intricate biochemical processes and essential steps for effective degradation in such systems have remained unclear. In this study, we harnessed the potential of the microbially driven Fenton reaction by employing Shewanella oneidensis MR-1 (MR-1). Our approach showcased remarkable efficacy in degrading a range of contaminants, including sulfadimethoxine (SDM), 4,4'-dibromodiphenyl ether (BDE-15) and atrazine (ATZ). Using SDM as a model contaminant of emergent contaminants (ECs), we unveiled that biodegradation relied on the generation of hydroxyl radicals (•OH) and involvement of oxidoreductases. Transcriptomic analysis shed light on the pivotal components of extracellular electron transfer (EET) during both anaerobic and aerobic periods. The presence of reactive oxidizing species induced cellular damage and impeded DNA repair, thereby affecting the Mtr pathway of EET. Moreover, the formation of vivianite hindered SDM degradation, underscoring the necessity of maintaining iron ions in the solution to ensure sustainable and efficient degradation. Overall, this study offers valuable insights into microbial technique for ECs degradation, providing a comprehensive understanding of degradation mechanisms during aerobic/anaerobic cycling.

Impact of mineral reactions and surface complexation on the transport of dissolved species in a subterranean estuary: Application of a comprehensive reactive transport modeling approach

Subterranean estuaries (STE) are hotspots of biogeochemical reactions. Here, dissolved constituents in waters of terrestrial and marine origin are transformed before they discharge to the coastal oceans. The involved biogeochemical reactions are complex and non-linear, calling for the application of numerical reactive transport modeling (RTM) to improve the process understanding. The aim of this study was to assess the roles of organic matter degradation and coupled secondary mineral reactions for the fate of dissolved species in STEs of sandy beaches. A comprehensive RTM approach was applied for this purpose, accounting for the effects of ion activities, pH, pe, redox reactions, mineral equilibria (calcite, goethite, siderite, iron sulfide, hydroxyapatite and vivianite) as well as surface complexation. Results show that the STE biogeochemistry and associated species fluxes are very sensitive to the assumed reaction network. For example, inorganic carbon and pH were largely controlled by calcite and siderite dynamics, and dissolved Fe2+ and HS- were precipitated as goethite, siderite and/or iron sulfides. Moreover, PO43- concentrations were affected by both the formation of vivianite or hydroxyapatite as well as surface complexation. This work helped to establish the relative importance of some of the major biogeochemical processes in the STE. However, further field studies are needed to understand which processes play a role in real-world STEs, including an exploration of the deep subsurface of STEs. Such field-based observations will improve our conceptual process understanding, which is key to developing well-constrained RTMs.

Fe(II)-driven spatiotemporal assembly of heterotrophic and anammox bacteria enhances simultaneous nitrogen and phosphorus removal for low-strength municipal wastewater

The mainstream anaerobic ammonium oxidation (anammox) faces considerable challenges with low-strength municipal wastewater. A Fe(Ⅱ)-amended partial denitrification coupled anammox (PD/A) process was conducted and achieved a long-term and efficient nitrogen and phosphorus removal, yielding effluent total nitrogen and phosphorus concentrations of 1.97 ± 1.03 mg/L and 0.23 ± 0.13 mg/L, respectively, which could well meet more stringent effluent discharge standard of some wastewater treatment plants in specific geographical locations, e.g., estuaries. Fe(Ⅱ)-driven vivianite formation provided key nucleuses for the optimization of the spatial distribution of heterotrophic and anammox bacteria with enhanced extracellular polymeric substances as key driving forces. Metagenomics analysis further revealed the increase of key genes, enhancing anammox bacteria homeostasis, which also bolstered the resistance to environmental perturbations. This study provided a comprehensive sight into the function of Fe(Ⅱ) in mainstream PD/A process, and explored a promising alternative for synergetic nitrogen and phosphorus removal for low-strength municipal wastewater treatment.

Performance of Fe-dosing membrane bioreactor and evaluation of phosphorus recovery as vivianite after long-term operation

In this study, the influence of high concentration of iron on the nutrient removal, membrane fouling and microbial diversity of membrane bioreactor for wastewater treatment were systematically investigated. Moreover, the potential of phosphorus recovery in the form of vivianite was assessed after the long-term operation. The results show that TP concentration in effluent was decreased to 1.07 ± 0.47 mg/L (without Fe addition), 0.41 ± 0.23 mg/L (Fe/P = 2), 0.20 ± 0.12 mg/L (Fe/P = 4). Compared with control group, the TN concentration in effluent was higher at the high concentration of iron, which was due to the decreased nitrite-oxidizing bacteria (NOB) by microbial population analysis. Membrane fouling was alleviated by enlarging floc size and reducing supernatant COD via adding iron. Besides, it was detected that the amorphous ferric oxide and Fe(III) bound phosphorus were the main Fe and P speciation and vivanite (ca. 29 %). The anaerobic environment was conducive to the formation of vivianite and the phosphorus recovery as vivanite was recommended based on the results of current study.

Tracking the formation potential of vivianite within the treatment train of full-scale wastewater treatment plants

Phosphorus recovery is a vital element for the circular economy. Wastewater, especially sewage sludge, shows great potential for recovering phosphate in the form of vivianite. This work focuses on studying the iron, phosphorus, and sulfur interactions at full-scale wastewater treatment plants (Viikinmäki, Finland and Seine Aval, France) with the goal of identifying unit processes with a potential for vivianite formation. Concentrations of iron(III) and iron(II), phosphorus, and sulfur were used to evaluate the reduction of iron and the formation potential of vivianite. Mössbauer spectroscopy and X-ray diffraction (XRD) analysis were used to confirm the presence of vivianite in various locations on sludge lines. The results show that the vivianite formation potential increases as the molar Fe:P ratio increases, the anaerobic sludge retention time increases, and the sulfate concentration decreases. The digester is a prominent location for vivianite recovery, but not the only one. This work gives valuable insights into the dynamic interrelations of iron, phosphorus, and sulfur in full-scale conditions. These results will support the understanding of vivianite formation and pave the way for an alternative solution for vivianite recovery for example in plants that do not have an anaerobic digester.

Strategies for optimizing biovivianite production using dissimilatory Fe(III)-reducing bacteria.

Vivianite (Fe3(PO4)2·8H2O), a sink for phosphorus, is a key mineralization product formed during the microbial reduction of phosphate-containing Fe(III) minerals in natural systems, and also in wastewater treatment where Fe(III)-minerals are used to remove phosphate. As biovivianite is a potentially useful Fe and P fertiliser, there is much interest in harnessing microbial biovivianite synthesis for circular economy applications. In this study, we investigated the factors that influence the formation of microbially-synthesized vivianite (biovivianite) under laboratory batch systems including the presence and absence of phosphate and electron shuttle, the buffer system, pH, and the type of Fe(III)-reducing bacteria (comparing Geobacter sulfurreducens and Shewanella putrefaciens). The rate of Fe(II) production, and its interactions with the residual Fe(III) and other oxyanions (e.g., phosphate and carbonate) were the main factors that controlled the rate and extent of biovivianite formation. Higher concentrations of phosphate (e.g., P/Fe = 1) in the presence of an electron shuttle, at an initial pH between 6 and 7, were needed for optimal biovivianite formation. Green rust, a key intermediate in biovivianite production, could be detected as an endpoint alongside vivianite and metavivianite (Fe2+Fe3+2(PO4)2.(OH)2.6H2O), in treatments with G. sulfurreducens and S. putrefaciens. However, XRD indicated that vivianite abundance was higher in experiments containing G. sulfurreducens, where it dominated. This study, therefore, shows that vivianite formation can be controlled to optimize yield during microbial processing of phosphate-loaded Fe(III) materials generated from water treatment processes.

Recovery of phosphorus from aqueous media as vivianite by crystallization

AbstractSince phosphorus resources are limited, optimal management of available phosphorus (P) and phosphorus recovery is a vital issue for the entire world. Studies continue on more efficient and economical phosphorus recovery techniques from wastewater and sludge. Recovery of phosphorus as vivianite is a current issue worldwide and studies are ongoing. Vivianite is a valuable mineral used in some industrial facilities and agricultural activities. Therefore, recovery of P from wastewater based on vivianite formation not only contributes to the sustainable use of phosphorus but also provides potential economic opportunities. In this study, it was aimed to determine the recovery potential of phosphorus as vivianite and to evaluate the effects of operational conditions on phosphorus recovery. For this purpose, two types of lab‐scale crystallizer, semibatch completely mixed and fluidized bed, were used. In experimental studies, the effects of operating parameters such as pH, Fe/P ratio, Fe feeding rate, and P concentration for vivianite crystallization were investigated. The highest phosphorus recovery was found at a Fe/P ratio of 1.8 and P removal efficiency of up to 69% was achieved by vivianite crystallization.

Phosphorus release and recovery by reductive dissolution of chemically precipitated phosphorus from simulated wastewater

Chemically mediated recovery of phosphorous (P) as vivianite from the sludges generated by chemical phosphorus removal (CPR) is a potential means of enhancing sustainability of wastewater treatment. This study marks an initial attempt to explore direct P release and recovery from lab synthetic Fe–P sludge via reductive dissolution using ascorbic acid (AA) under acidic conditions. The effects of AA/Fe molar ratio, age of Fe–P sludge and pH were examined to find the optimum conditions for Fe–P reductive solubilization and vivianite precipitation. The performance of the reductive, chelating, and acidic effects of AA toward Fe–P sludge were evaluated by comparison with hydroxylamine (reducing agent), oxalic acid (chelating agent), and inorganic acids (pH effect) including HNO3, HCl, and H2SO4. Full solubilization of Fe–P sludge and reduction of Fe3+ were observed at pH values 3 and 4 for two Fe/AA molar ratios of 1:2 and 1:4. Sludge age (up to 11 days) did not affect the reductive solubilization of Fe–P with AA addition. The reductive dissolution of Fe–P sludge with hydroxylamine was negligible, while both P (95 ± 2%) and Fe3+ (90 ± 1%) were solubilized through non-reductive dissolution by oxalic acid treatment at an Fe/oxalic acid molar ratio 1:2 and a pH 3. With sludge treatment with inorganic acids at pH 3, P and Fe release was very low (<10%) compared to AA and oxalic acid treatment. After full solubilization of Fe–P sludge by AA treatment at pH 3 it was possible to recover the phosphorus and iron as vivianite by simple pH adjustment to pH 7; P and Fe recoveries of 88 ± 2% and 90 ± 1% respectively were achieved in this manner. XRD analysis, Fe/P molar ratio measurements, and magnetic attraction confirmed vivianite formation. PHREEQC modeling showed a reasonable agreement with the measured release of P and Fe from Fe–P sludge and vivianite formation.

The Impact of Phosphorus Level on Vivianite Precipitation during Microbial Reduction of Ferrihydrite

Iron minerals play a pervasive role in the cycling of phosphorus (P) within both terrestrial and aquatic environments. The behavior of P, especially in oxygen-depleted environments, is frequently regulated by changing redox conditions and the associated phase transformations of Fe (III) (hydr)oxides (Borch and Fendorf 2007). Although the stability of Fe (III) hydroxides under changing redox conditions is well established, the relationship between specific minerals and their influence on the mechanisms of P retention and release remain unclear. In particular, the minerals vivianite (Fe3(PO4)2·8H2O) and ferrihydrite (Fe2O3·0.5H2O) are of interest. Vivianite crystallization in sediments has attracted increasing attention as a major contributor to P retention during early diagenesis (Slomp et al. 2013) and ferrihydrite reduction has been linked to fluctuating P concentrations which can impact vivianite crystallization. Additionally, there exists strong biological controls on these minerals as the reduction of Fe (III) oxides by dissimilatory iron-reducing bacteria may result in the formation of a suite of Fe (II)-bearing secondary minerals (O’Loughlin et al. 2021). To better understand the biogeochemical mechanisms behind these interactions, we examined the effects of fluctuating P concentrations on the reduction of ferrihydrite by Shewanella putrefaciens CN32 and resulting vivianite formation. In this study, bio-reduction experiments were conducted under sterile conditions in serum bottles containing 80 mL of mineral medium, with 80 mM Fe (III) in the form of Ferrihydrite, and various P concentrations (0, 1 mM, and 10 mM). The bottles were placed on a roller drum (180 rpm) and incubated at 30 oC in the dark for 15 days. Dissolved Fe (II), P concentrations, pH, and optical density (OD) values throughout the experiments were also measured. Our results showed that during incubation, Shewanella putrefaciens CN32 accelerated Ferrihydrite reduction as the dissolved iron (Fe2+) concentration increased significantly when compared to other bacterial and ferrihydrite treatments, as well as the control treatment. Additionally, P in both the 1mM and 10mM treatments was depleted after 5 and 7 days, respectively, and resulted in crystalline precipitates. Scanning electron microscopy (SEM) analyses of precipitates showed well-formed and highly crystalline vivianite particles of up to 30 µm in length in high P level. Some crystalline precipitates were confirmed as vivianite through SEM and Raman spectroscopy matching a known vivianite reference (Taylor et al. 2008), but only within the 10mM P incubations. After 15 days of incubation the morphology of the vivianite changed from aggregates of lath-shaped crystals to acicular crystals (Fig. 1). Based on our results, fluctuating P concentrations do indeed have a pronounced effect on ferrihydrite reduction and thus vivianite formation.

Phosphate burial in aquatic sediments: Rates and mechanisms of vivianite formation from mackinawite

Excess phosphorus abundance often drives eutrophication and affects surface water quality. Formation of vivianite (Fe3(PO4)2 • 8H2O) in aquatic sediments acts as a significant sink for phosphate (P), crucial for resorting surface waters. Authigenic vivianite formation, however, can be limited by other ferrous iron containing phases, in particular iron sulfides. Although thermodynamically feasible under suitable conditions, the formation of vivianite from mackinawite has been widely disregarded for authigenic phosphate mineral formation. Here we investigated the formation of vivianite from mackinawite (FeS) in batch experiments in which dissolved sulfide was continuously removed, at P levels between 0 – 5 mM in a pH of 6 to 8. Solid characterizations by electron microscopy, X-ray diffraction as well as Mössbauer and X-ray absorption spectroscopy demonstrates that vivianite was formed at all pH values in P amended experiments. The temporal evolution of dissolved Fe(II) concentrations indicates that the transformation proceeds via the release of the dissolved Fe(II) by FeS dissolution and subsequent vivianite precipitation, over time scales of days. The kinetics of the transformation are controlled by the dissolution rates of FeS. Aging and transformation of FeS, however, compete with vivianite formation. Aging is more pronounced at higher pH but is inhibited by P adsorption. Hence, the effect of pH and P concentration on aging is the main reason for the influence on these parameters on the rates and extent of vivianite formation. Our findings demonstrate that FeS can be an effective iron source for vivianite formation in aquatic sediments when sulfide concentrations decrease due to, for example, changes in external forcing or microbial sulfide oxidation. Formation of vivianite from FeS as an Fe source can also open new perspectives in P recovery in water treatment, for example when Fe is added to digesters to bind H2S.

Sedimentary phosphorus burial in three contrasting boreal lakes in Finland

AbstractPermanent phosphorus (P) burial in sediment regulates lake trophic state over long timescales, but the controls on P burial are only partially understood. A diversity of biogeochemical settings may be found in lake sediments, which may have a strong impact on the processes controlling P burial from one location to another. Here, we investigate early diagenesis of P in three contrasting lakes in Southwest Finland. Eutrophic Lake Köyliönjärvi and mesotrophic Lake Pyhäjärvi have a history of nutrient loadings from agriculture, while Lake Vähäjärvi is an oligotrophic small forest lake, leading to potentially contrasting sediment biogeochemical dynamics. We combined porewater data and solid-phase sediment geochemical data to identify P phases in each system and investigate the dominant processes controlling P burial. Porewater profiles showed opposite gradients between the oligotrophic and the mesotrophic/eutrophic systems, implying net diffusive fluxes into and out of the sediments, respectively. Furthermore, sediment P data showed contrasting P speciation. Reactive P is buried in all systems, but the role of reducible iron (Fe) oxides in P retention is greater in mesotrophic/eutrophic lakes. In the oligotrophic system, aluminium (Al) oxides controlled P sorption into the sediment after diffusion from lake water. Evidence for vivianite formation was found only in the mesotrophic Lake Pyhäjärvi sediment, where 42–47% of total P was released in a Fe(II)-P specific extraction from the deeper part of the sediment column and vivianite crystals could be isolated from sediment samples.

Deciphering the interaction of heavy metals with Geobacter-induced vivianite recovery from wastewater

Vivianite recovery from wastewater driven by Geobacter is one of the promising approaches to address the challenges of phosphorus (P) resource shortage and eutrophication. However, the interfere of heavy metals which are prevalent in many actual wastewater with this process is rarely reported. In this study, we investigated the impact of heavy metals (i.e., Cu and Zn ions) on microbial activity, Fe reduction, P recovery efficiency, and their fate during Geobacter-induced vivianite recovery process. The experimental results showed that low and medium concentrations of Cu and Zn prolonged the Fe reduction and P recovery time but had little effect on the final P recovery efficiency. However, high concentrations of Cu and Zn ultimately inhibit vivianite formation. In addition, the different concentrations of Cu and Zn showed different effects on the morphology of the recovered vivianite. The migration of Cu and Zn was analysed by stepwise extraction of heavy metals in the vivianite. Medium concentrations of Cu and Zn were more likely to co-precipitate with vivianite, while adsorption was the primary mechanism at low concentrations. Furthermore, there were differences in the fate of Cu and Zn, and a competition mechanism was observed. Finally, we found that increasing the Fe/P ratio can significantly reduce the residues of heavy metals in vivianite. It also increased the adsorbed Cu and Zn proportion and reduced co-precipitation. These results provide insights into improving the efficiency of vivianite recovery and managing the environmental risks of heavy metal in the recovered product.

BOTTOM SEDIMENTS OF SURFACE WATERCOURSES OF THE MALMYZHSKY MOUNTAIN RANGE

X-ray fluorescence, electron microscopic, sedimentation analyses and laser diffractometry methods were used to study the composition of bottom sediments of surface watercourses of the Malmyzhskaya Ridge section allocated for the construction of a mining and processing plant (Khabarovsk region, Russia). It is established that the bottom sediments of the coastal zone of the watercourses of the studied area are characterized by a similar gross composition and physical and chemical properties (pH, solid phase density, total carbon content, wetting edge angle CAW). Th ey are mainly represented by fine earth with a high proportion of suspended sediments, in which the fraction of coarse silt prevails (particle size &lt;2,0 mm, &lt;0,1 mm and 0,01-0,05 mm, respectively). It is shown that deforestation in the sources of watercourses accompanied by soil erosion leads to a significant increase in the dispersion of sediments (an increase in the proportion of suspended sediments up to 90%) in the upstream. Downstream, with the distance from the felling sites, the infl uence of deforestation on the dispersion of deposits fades. Th e content of suspended sediment is reduced to values characteristic of watercourses in the catchment area of which deforestation has not been carried out. Significant microaggregation of suspended sediments of watercourses was revealed, the participation of microbiota (testate amoebas of xenosome taxa, diatoms and Fereducing bacteria) in the formation of microaggregates was diagnosed. Th e latter are involved in the formation of vivianite on the surface of ferruginous-clay microaggregates with an increased content of phosphates after fires. The mechanism of formation of toroidal microforms of vaterite in bottom sediments with the participation of cyanobacteria of the Spirulinaceae family is proposed.

AQDS-mediated dissimilatory reduction of iron (hydr)oxides induces the formation of large grain vivianite: A new insight for phosphorus pollution control in sediment

Quinones plays a crucial role in iron (hydr)oxides dissimilatory reduction and the geochemical cycle of elements. However, the interfacial reactions and the subsequent effect of phosphorus (P) in sediments remain unclear. To clarify it, 9,10-anthraquinone-2,6-disulfonic acid (AQDS) was used to participate in reduction of hematite and goethite by Geobacter metallireducens GS-15, and the interfacial electron transfer between iron (hydr)oxides and AQDS were also explained. Results showed that AQDS had a higher promotion effect on the reduction of goethite than hematite, and more than 41% of goethite was reduced compared to the control check, with an 80.6 mg g−1 phosphorus immobilized. Vivianite was produced in this system, and the size of vivianite in hematite-AQDS and goethite-AQDS groups increased 7.59% and 57.78%, respectively, compared to the corresponding groups without AQDS. The highest weight of vivianite-P was in the Goe-AQDS group by X-ray absorption near edge structure (XANES). Electrochemical characteristics showed that the interfacial electron transfer rates of hematite and goethite with AQDS adding were 7.49 s−1 and 9.03 s−1, respectively. Therefore, high electron transfer efficiency led more microbial iron reductions, which generated high concentrations of Fe(Ⅱ) and facilitated the increasing of production and grain size of vivianite. These findings provide a new understanding of vivianite generation and phosphorus immobilization.

The formation of authigenic phosphorus minerals in cold-seep sediments from the South China Sea: Implications for carbon cycling below the sulfate-methane transition

The formation of authigenic phosphorus (P) minerals near the sulfate-methane transition (SMT) represents an important pathway of P burial in marine sediments. However, our current understanding of the coupling between the formation of authigenic phosphate and carbon and iron (Fe) cycling is insufficient. In this study, a piston core recovered from the Haima cold seeps of the Qiongdongnan basin, northern South China Sea, was used to analyze pore-water parameters and solid-phase Fe and P speciation. Results from a previous study indicate that the current SMT is located at approximately 1 m below the seafloor (mbsf) and a fossil SMT located at approximately 6.5 mbsf. Dissolved phosphate concentrations and solid-phase iron oxide (FeOx) contents are found to decrease with depth, while Fe-bound P (PFe) and authigenic phosphate (PAuth) contents increase with depth in the zone between the current and fossil SMTs where gas hydrate is present, suggesting that vivianite and authigenic apatite formed in this zone. Gas hydrate below the current SMT will dissociate once methane is undersaturated, which could persistently provide dissolved methane to prevent the downward shift of the current SMT where methane is continually consumed. Such a methane-rich environment maintained by gas hydrate may favor the persistent reduction of FeOx and the formation of vivianite. Dissolved phosphate concentrations are high, but decrease rapidly with depth at the fossil SMT. Combined with higher FeOx and PAuth contents and lower PFe contents and lower POrg/total organic carbon (TOC) ratios, these results suggest the formation of authigenic apatite at the fossil SMT. The high dissolved phosphate concentration and low POrg/TOC ratios at the fossil SMT are interpreted to reflect preferential release of P during the degradation of organic matter generated by methanotrophic microorganisms. Overall, our study shows that P speciation in methane-rich sediments provides insight into the formation processes of authigenic P minerals near the SMT and associated carbon and Fe cycling processes.

Nucleation and Crystallization of Ferrous Phosphate Hydrate via an Amorphous Intermediate.

The fundamental processes of nucleation and crystallization are widely observed in systems relevant to material synthesis and biomineralization; yet most often, their mechanism remains unclear. In this study, we unravel the discrete stages of nucleation and crystallization of Fe3(PO4)2·8H2O (vivianite). We experimentally monitored the formation and transformation from ions to solid products by employing correlated, time-resolved in situ and ex situ approaches. We show that vivianite crystallization occurs in distinct stages via a transient amorphous precursor phase. The metastable amorphous ferrous phosphate (AFEP) intermediate could be isolated and stabilized. We resolved the differences in bonding environments, structure, and symmetric changes of the Fe site during the transformation of AFEP to crystalline vivianite through synchrotron X-ray absorption spectroscopy at the Fe K-edge. This intermediate AFEP phase has a lower water content and less distorted local symmetry, compared to the crystalline end product vivianite. Our combined results indicate that a nonclassical, hydration-induced nucleation and transformation driven by the incorporation and rearrangement of water molecules and ions (Fe2+ and PO43-) within the AFEP is the dominating mechanism of vivianite formation at moderately high to low vivianite supersaturations (saturation index ≤ 10.19). We offer fundamental insights into the aqueous, amorphous-to-crystalline transformations in the Fe2+-PO4 system and highlight the different attributes of the AFEP, compared to its crystalline counterpart.