The nature of reactive intermediates and the mechanism of the cis-dihydroxylation of arenes and olefins by Rieske dioxygenases and synthetic nonheme iron catalysts have been the topic of intense research over the past several decades. In this study, we report that a spectroscopically well characterized mononuclear nonheme iron(III)-peroxo complex reacts with olefins and naphthalene derivatives, yielding iron(III) cycloadducts that are isolated and characterized structurally and spectroscopically. Kinetics and product analysis reveal that the nonheme iron(III)-peroxo complex is a nucleophile that reacts with olefins and naphthalenes to yield cis-diol products. The present study reports the first example of the cis-dihydroxylation of substrates by a nonheme iron(III)-peroxo complex that yields cis-diol products.

Manganese (Mn) is an abundant element in terrestrial and coastal ecosystems and an essential micronutrient in the metabolic processes of plants and animals. Mn is generally not considered a potentially toxic element due to its low content in both soil and water. However, in coastal ecosystems, the Mn dynamic (commonly associated with the Fe cycle) is mostly controlled by redox processes. Here, we assessed the potential contamination of the Rio Doce estuary (SE Brazil) by Mn after the world’s largest mine tailings dam collapse, potentially resulting in chronic exposure to local wildlife and humans. Estuarine soils, water, and fish were collected and analyzed seven days after the arrival of the tailings in 2015 and again two years after the dam collapse in 2017. Using a suite of solid-phase analyses including X-ray absorption spectroscopy and sequential extractions, our results indicated that a large quantity of Mn II arrived in the estuary in 2015 bound to Fe oxyhydroxides. Over time, dissolved Mn and Fe were released from soils when Fe III oxyhydroxides underwent reductive dissolution. Due to seasonal redox oscillations, both Fe and Mn were then re-oxidized to Fe III , Mn III , and Mn IV and re-precipitated as poorly crystalline Fe oxyhydroxides and poorly crystalline Mn oxides. In 2017, redox conditions (Eh: −47 ± 83 mV; pH: 6.7 ± 0.5) favorable to both Fe and Mn reduction led to an increase (~880%) of dissolved Mn (average for 2015: 66 ± 130 μg L −1 ; 2017: 582 ± 626 μg L −1 ) in water and a decrease (~75%, 2015: 547 ± 498 mg kg −1 ; 2017: 135 ± 80 mg kg −1 ) in the total Mn content in soils. The crystalline Fe oxyhydroxides content significantly decreased while the fraction of poorly ordered Fe oxides increased in the soils limiting the role of Fe in Mn retention. The high concentration of dissolved Mn found within the estuary two years after the arrival of mine tailings indicates a possible chronic contamination scenario, which is supported by the high levels of Mn in two species of fish living in the estuary. Our work suggests a high risk to estuarine biota and human health due to the rapid Fe and Mn biogeochemical dynamic within the impacted estuary.

Vanadium is a redox-active metal that has been added to the EPA's Contaminant Candidate List with a notification level of 50 μg L −1 due to mounting evidence that V V exposure can lead to adverse health outcomes. Groundwater V concentration exceeds the notification level in many locations, yet geochemical controls on its mobility are poorly understood. Here, we examined the redox interaction between V IV and birnessite (MnO 2 ), a wellcharacterized oxidant and a scavenger of many trace metals. In our findings, birnessite quickly oxidized sparingly soluble V IV species such as haggite [V 2 O 3 (OH) 2 ] into highly mobile and toxic vanadate (H n VO 4(3−n)− ) in continuously stirred batch reactors under neutral pH conditions. Synchrotron X-ray absorption spectroscopic (XAS) analysis of in situ and ex situ experiments showed that oxidation of V IV occurs in two stages, which are both rapid relative to the measured dissolution rate of the V IV solid. Concomitantly, the reduction of birnessite during V IV oxidation generated soluble Mn II , which led to the formation of the Mn III oxyhydroxide feitknechtite (β-MnOOH) upon back-reaction with birnessite. XAS analysis confirmed a bidentate-mononuclear edge-sharing complex formed between V V and birnessite, although retention of V V was minimal relative to the aqueous quantities generated. In summary, we demonstrate that Mn oxides are effective oxidants of V IV in the environment with the potential to increase dissolved V concentrations in aquifers subject to redox oscillations.

Manganese and arsenic both threaten groundwater quality globally, but their chemical behavior leads to both co-contamination and separation of these contaminants from individual well to regional scales. Here we tested manganese and arsenic retention under conditions commonly found within aquifer redox fluctuating and transition zones where both arsenic and iron phases are present in oxidized forms, but manganese persists as reduced and soluble Mn­(II). Analysis of column aqueous breakthrough data and characterization of solid-phase products using X-ray photoelectron (XPS) and absorption spectroscopies (XAS) show that the addition of bicarbonate increased manganese retention but decreased arsenic retention, while the presence of manganese and arsenic together increased both arsenic and manganese retention. In the presence of O2 arsenic remained oxidized as arsenate under all conditions measured; however, reduced Mn­(II) was oxidized to an average Mn oxidation state of ∼3 in the absence of arsenate. The presence of arsenate partially inhibited Mn­(II) oxidation likely by blocking ferrihydrite surfaces needed to catalyze Mn­(II) oxidation by O2 and by stabilizing Mn­(II) via ternary complex formation. These results highlight the interactions between reduced and oxidized contaminants that can contribute to the co-occurrence or physical separation of manganese and arsenic in groundwater systems under changing or stratified redox conditions.

Ceramic water filters (CWFs) are produced globally using local clay sources and can effectively remove bacterial pathogens during point-of-use water treatment. The ceramic production process involves firing clay mixed with burnout material at temperatures of 800–1100 °C, which induces mineralogical changes leading to increased arsenic (As) leaching from CWF material compared to source clay. Unfired clay and fired CWFs from Cambodia, Canada, and Mexico, CWF from Laos, and test-fired clay from the United States were analyzed to determine the extent of As leaching from CWFs that range in As (<1 to 16 mg kg–1) and iron (Fe) (0.6 to 5%) content. Deionized water, NaOH, HCl, and oxalate extractions showed that firing increased As solubility and decreased Fe solubility compared to unfired clay, with up to 8 mg kg–1 of water-soluble As in Cambodian CWFs. X-ray absorption spectra of the Cambodian clay and CWF showed a decrease in the Fe–O distance from 2.01 to 1.91 Å and decreased Fe coordination number from 6.3 to 4.6 after firing, indicating a decrease in Fe–O coordination. Arsenic­(V) was the dominant species in Cambodia clay and CWF, existing primarily as a surface complex with average As–Fe distance of 3.28 Å in clay while in CWF As was either an outer-sphere As­(V) phase or a discrete arsenate phase with no significant As–Fe scattering contribution within the resolution of the data. Improved understanding of molecular-scale processes that cause increased As leaching from CWFs provides a basis for assessing As leaching potential prior to CWF factory capital investment as well as engineered solutions (e.g., modified firing temperature, material amendments, and leaching prior to distribution) to mitigate As exposure from CWFs.

Anthropogenic emissions of vanadium (V) into terrestrial and aquatic surface systems now match those of geogenic processes, and yet, the geochemistry of vanadium is poorly described in comparison to other comparable contaminants like arsenic. In oxic systems, V is present as an oxyanion with a +5 formal charge on the V center, typically described as H x VO 4 (3– x )– , but also here as V(V). Iron (Fe) and manganese (Mn) (oxy)hydroxides represent key mineral phases in the cycling of V(V) at the solid–solution interface, and yet, fundamental descriptions of these surface-processes are not available. Here, we utilize extended X-ray absorption fine structure (EXAFS) and thermodynamic calculations to compare the surface complexation of V(V) by the common Fe and Mn mineral phases ferrihydrite, hematite, goethite, birnessite, and pyrolusite at pH 7. Inner-sphere V(V) complexes were detected on all phases, with mononuclear V(V) species dominating the adsorbed species distribution. Our results demonstrate that V(V) adsorption is exergonic for a variety of surfaces with differing amounts of terminal −OH groups and metal–O bond saturations, implicating the conjunctive role of varied mineral surfaces in controlling the mobility and fate of V(V) in terrestrial and aquatic systems.

The Wood−Ljungdahl Pathway is a unique biological mechanism of carbon dioxide and carbon monoxide fixation proposed to operate through nickel-based organometallic intermediates. The most unusual steps in this metabolic cycle involve a complex of two distinct nickel−iron−sulfur proteins: CO dehydrogenase and acetyl-CoA synthase (CODH/ACS). Here, we describe the nickel-methyl and nickel-acetyl intermediates in ACS completing the characterization of all its proposed organometallic intermediates. A single nickel site (Ni p ) within the A cluster of ACS undergoes major geometric and redox changes as it transits the planar Ni p , tetrahedral Ni p −CO and planar Ni p −Me and Ni p −Ac intermediates. We propose that the Ni p intermediates equilibrate among different redox states, driven by an electrochemical−chemical (EC) coupling process, and that geometric changes in the A-cluster linked to large protein conformational changes control entry of CO and the methyl group.

This study investigated the reaction kinetics on the oxidative transformation of lead(ii) minerals by free chlorine (HOCl) and free bromine (HOBr) in drinking water distribution systems.