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Short-range-ordered Fe(III) minerals such as ferrihydrite (Fh) are ubiquitous in the environment, are key players in biogeochemical cycling, and sorb trace elements and nutrients. As such, it is important to be able to identify the presence of such minerals in natural samples. Fh is commonly observed to be X-ray amorphous and cannot be easily analyzed using X-ray diffraction, meaning that spectroscopic methods such as X-ray absorption or 57Fe Mössbauer spectroscopy (MBS) are necessary for accurate identification and quantification. Despite decades of research into Fh using MBS, there is a discrepancy in the literature about the exact parameters applicable to the mineral when measured at liquid helium temperature. Fh is frequently fitted with either one, two, or three hyperfine sextets with little interpretation applied to the meaning of each, which is problematic as a one sextet model does not account for the asymmetric lineshape frequently observed for Fh. Here, we address inconsistencies in the fitting of Fh and provide a more standardized approach to its identification by MBS. We present a systematic comparison of different fitting methods, notably based on Lorentzian and Voigt functions. We suggest that the most suitable approach to fitting pure Fh at liquid helium temperature is with two sextets (A and B) fitted using an extended Voigt-based function with the ability to apply probability distributions to each hyperfine parameter. 2-line Fh: A (δ = 0.49 mm/s; ε = 0.00 mm/s; Bhf = 50.1 T) and B (δ = 0.42 mm/s; ε = –0.01 mm/s; Bhf = 46.8 T) 6-line Fh: A (δ = 0.50 mm/s; ε = –0.03 mm/s; Bhf = 50.2 T) and B (δ = 0.40 mm/s; ε = –0.05 mm/s; Bhf = 47.1 T). We interpret the two sextets to be due to either differences in the coordination environment of iron, i.e., in tetrahedral or octahedral sites, the presence of a disordered surface phase, or a combination of both. We hope that provoking a discussion on the use of MBS for Fh will help develop a greater understanding of this mineral, and other short-range ordered iron minerals, which are so important in environmental processes.

With global warming and alterations of climatic patterns, greater frequency and severity of extreme events are observed in different regions. Drought is one of the most challenging extreme events, one which can cause catastrophic and long-lasting impacts on water availability, environment, agriculture, economy, and societies. This study investigates the historic changes of drought conditions in Southern Alberta which is home to communities whose main economic activity is agriculture, or otherwise related to environmental variables, and has experienced severe droughts in the past. We employed SPI (standardized precipitation index) and SPEI (standardized precipitation-evapotranspiration index) as drought indicators at 1-, 3-, 6-, 9-, and 12-month(s) timescales, to explore significant changes during 1980–2018. The indices were computed using a Daymet-gridded dataset for the South Saskatchewan River Watershed (SSRW). Constructed drought occurrence maps revealed that, on average, in nearly half of the analysis period, the region experienced drought. Comparing four past decades showed that drought impacted a larger area in 2000–2010, and the percentage of the area impacted by severe or extreme droughts significantly increased in the last two decades, compared to 1980–2000. Results show decreasing trends of drought in some areas, mainly in the headwaters of Bow River in the Rocky Mountains, and increasing trends in larger areas, mostly found downstream. The result denotes expansion of the dry/wet conditions to larger areas at longer timescales. The extent of areas with a significant trend (increasing/decreasing) was greater with longer timescales of drought indices. Comparing the two drought indices suggests significant differences, and outperformance of SPEI in detecting dry conditions.

Microbial electrosynthesis is an emerging biosynthesis technology that produces value-added chemicals and fuels and, at the same time, reduces the environmental carbon footprint. However, constraints, such as low current densities and high inner resistance, disfavor this technology for industrial-scale purposes. The cathode performance has been strongly improved in recent years, while the anode performance has not been given enough attention despite its importance in closing the electric circuit. For traditional water electrolysis, O2 is produced at the anode, which is toxic to the anaerobic autotrophs that engage in microbial electrosynthesis. To overcome O2 toxicity in conventional microbial electrosynthesis, the anode and the cathode chamber have been separated by an ion-exchange membrane to avoid contact between the microbes and O2. However, ionexchange membranes increase the maintenance costs and compromise the production efficiency by introducing an additional internal resistance. Furthermore, O2 is inevitably transferred to the catholyte due to diffusion and electro-osmotic fluxes that occur within the membrane. Here, we proved the concept of integrating carbon oxidation with sacrificial anodes and microbes to simultaneously inhibit the O2 evolution reaction (OER) and circumvent membrane application, which allows microbial electrosynthesis to proceed in a single chamber. The carbon-based anodes performed carbon oxidation as the alternative reaction to the OER. This enables microbial electrosynthesis to be performed with cell voltages as low as 1.8-2.1 V at 10 A·m-2. We utilized Methanothermobacter thermoautotrophicus ΔH in a single-chamber Bioelectrochemical system (BES) with the best performing carbon-based anode (i.e., activated-carbon anode with soluble iron) to achieve a maximum cathode-geometric CH4 production rate of 27.3 L·m-2·d-1, which is equal to a volumetric methane production rate of 1.1·10−1 L·L-1·d-1 in our BES, at a coulombic efficiency of 99.4%. This proof-of-concept study allows microbial electrosynthesis to be performed more energy-efficiently and can be immediately utilized for research purposes in the microbial electrosynthesis field of study.

This article addresses a deceptively simple two-part question: what are the desired core skills obtained by completing the requirements for an undergraduate degree in criminal justice? And is it po...

STUDY QUESTION Which chemotherapeutic agents and body site-specific radiation fields are dose-dependently associated with an increased risk of fertility impairment in long-term female childhood, adolescent and young adulthood (CAYA) cancer survivors? SUMMARY ANSWER Busulfan, lower abdominal radiotherapy (RT) and total body irradiation (TBI) seem to be associated with fertility impairment at any dose, whereas gonadotoxicity of melphalan and procarbazine is suggested at medium/high (>140 mg/m2) or high dose (>5600 mg/m2) therapy, respectively. WHAT IS KNOWN ALREADY Several treatment-related fertility deficits, as assessed by both self-reported outcomes and hormonal markers are known to occur following treatment of CAYA cancer. However, knowledge regarding precise dose-related estimates of these treatment-related risks are scarce. STUDY DESIGN, SIZE, DURATION The current case–control study was nested within the PanCareLIFE cohort study. In total, 1332 CAYA survivors from 8 countries, 9 institutions and 11 cohorts, participated in and contributed data to the study. PARTICIPANTS/MATERIALS, SETTING, METHODS All participants were female 5-year CAYA cancer survivors. In total, 450 cases (fertility impaired survivors) and 882 matched controls (not fertility impaired survivors) were included. Fertility impairment was defined using both questionnaire data (primary or secondary amenorrhea; use of artificial reproductive techniques; unfulfilled wish to conceive) and hormonal data (FSH and anti-Müllerian hormone (AMH)). Multivariable logistic regression models were used to investigate the effect of (i) alkylating agent exposure, and (ii) dose categories for individual chemotherapeutic agents and for RT-exposed body sites. MAIN RESULTS AND THE ROLE OF CHANCE A positive dose–effect relationship between cyclophosphamide equivalent dose (CED) score and fertility impairment was found, with survivors with a CED score > 7121 mg/m2 being at a significantly increased risk of fertility impairment (odds ratio (95% CI) = 2.6 (1.9–3.6) P 140 mg/m2) or high dose (>5600 mg/m2) therapy, respectively. LIMITATIONS, REASONS FOR CAUTION Our study may have been subject to selection bias since data from about half of the original base cohorts were available for the current study. This could impact the generalizability of our study results. WIDER IMPLICATIONS OF THE FINDINGS We identified survivors at high risk for fertility impairment and, consequently, for a reduced or even absent reproductive life span. Both girls and young women who are about to start anti-cancer treatment, as well as adult female survivors, should be counselled about future parenthood and referred to a reproductive specialist for fertility preservation, if desired. STUDY FUNDING/COMPETING INTEREST(S) This study has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement no. 602030. There are no competing interests. TRIAL REGISTRATION NUMBER n/a

Redox-driven biogeochemical element cycles play a central role in converting organic matter in aquatic ecosystems. They also perform key functions such as removing nitrate, mitigating the formation of greenhouse gases and weakening the effects of contaminants. Recent research has revealed the presence of redox-active compounds in these ecosystems with hitherto unknown redox properties. These substances are metastable (that is, non-equilibrium solid phases), which can both donate and accept electrons. They are highly redox reactive and recyclable and may act as biogeobatteries by temporarily storing electrons. Their lifetime, however, is limited, and with time they become more crystalline and less reactive. In this Review, we argue that these redox-active metastable phases require activation by fluctuating redox conditions to maintain their high reactivity. In aquatic ecosystems, switching between oxidizing and reducing conditions can be achieved only through hydrological perturbations at hydrological interfaces (for example, water level fluctuations). We present a novel framework that links microscale biogeochemical processes to large-scale hydrological processes, and discuss implications and future research directions for biogeochemical element cycles in aquatic systems exposed to frequent hydrological disturbances. Highly redox-active compounds play an important role in biogeochemical element cycles in aquatic systems that are exposed to frequent hydrological disturbances.

The oxygenation of early Earth’s atmosphere during the Great Oxidation Event, is generally accepted to have been caused by oceanic Cyanobacterial oxygenic photosynthesis. Recent studies suggest that Fe(II) toxicity delayed the Cyanobacterial expansion necessary for the GOE. This study investigates the effects of Fe(II) on two Cyanobacteria, Pseudanabaena sp. PCC7367 and Synechococcus sp. PCC7336, in a simulated shallow-water marine Archean environment. A similar Fe(II) toxicity response was observed as reported for closed batch cultures. This toxicity was not observed in cultures provided with continuous gaseous exchange that showed significantly shorter doubling times than the closed-culture system, even with repeated nocturnal addition of Fe(II) for 12 days. The green rust (GR) formed under high Fe(II) conditions, was not found to be directly toxic to Pseudanabaena sp. PCC7367. In summary, we present evidence of diurnal Fe cycling in a simulated shallow-water marine environment for two ancestral strains of Cyanobacteria, with increased O2 production under anoxic conditions., Cyanobacterial photosynthesis is thought to have oxygenated Earth’s atmosphere during the Great Oxidation Event, but these organisms had to overcome the toxic effects of iron. Here the authors simulate Archaean conditions in Cyanobacterial cultures and find that gas exchange and rust formation alleviated iron toxicity.

Iron minerals are the most important arsenic host in As-contaminated deltaic sediments. Arsenic release from Fe minerals to groundwater exposes millions of people worldwide to a severe health threat. To understand the coupling of Fe mineralogy with As (im)mobilization dynamics, we analyzed the geochemistry and mineralogy of a 46 m long sediment core drilled into the redox transition zone where a high As Holocene aquifer is juxtaposed to a low As Pleistocene aquifer in the Red River delta, Vietnam. We specifically concentrated on mm- to cm-scale redox interfaces within the sandy aquifer. Various Fe phases, such as Fe- and Mn- bearing carbonates, pyrite, magnetite, hematite and Fe-hydroxides (goethite, lepidocrocite) with distinct As concentrations were identified by a combination of high-resolution microscopic, magnetic and spectroscopic methods. The concentration of As and its redox species in the different Fe-minerals were quantified by microprobe analysis and synchrotron X-ray absorption. We developed a conceptual model integrating Fe-mineral transformations and related As (im)mobilization across the redox interfaces. Accordingly, As is first mobilized via the methanogenic dissolution of Fe(III) (oxyhydr)oxide mineral coatings on sand grains when reducing groundwater from the Holocene aquifer intruded into the Pleistocene sands. This stage is followed by the formation of secondary Fe(II)-containing precipitates (mainly Fe- and Mn-bearing carbonates with relatively low As

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 (Hg0) and escape to the atmosphere or converted to methylmercury (MeHg), a potent neurotoxin that accumulates in food webs. FeII-bearing minerals such as magnetite, green rusts, siderite, and mackinawite are recognized HgII reducers. Another potentially Hg-reducing mineral, which commonly occurs in Fe- and organic/P-rich sediments and soils, is the ferrous iron phosphate mineral vivianite (FeII3(PO4)2·8H2O), but its reaction with HgII has not been studied to date. Here, nanoparticulate vivianite (particle size ∼ 50 nm; FeII content > 98%) was chemically synthesized and characterized by a combination of chemical, spectroscopic, and microscopic analyses. Its ability to reduce HgII was investigated at circumneutral pH under anoxic conditions over a range of FeII/HgII ratios (0.1–1000). For FeII/HgII ratios ≥1, which are representative of natural environments, HgII was very quickly and efficiently reduced to Hg0. The ability of vivianite to reduce HgII was found to be similar to those of carbonate green rust and siderite, two of the most effective Hg-reducing minerals. Our results suggest that vivianite may be involved in abiotic HgII reduction in Fe and organic/P-rich soils and sediments, potentially contributing to Hg evasion while also limiting MeHg formation in these ecosystems., Environmental Science & Technology, 55 (5), ISSN:0013-936X, ISSN:1520-5851

Scanning helium-ion microscopy (HIM) is an imaging technique with sub-nanometre resolution and is a powerful tool to resolve some of the tiniest structures in biology. In many aspects, the HIM resembles a field-emission scanning electron microscope (FE-SEM), but the use of helium ions rather than electrons provides several advantages, including higher surface sensitivity, larger depth of field, and a straightforward charge-compensating electron flood gun, which enables imaging of non-conductive samples, rendering HIM a promising high-resolution imaging technique for biological samples. Starting with studies focused on medical research, the last decade has seen some particularly spectacular high-resolution images in studies focused on plants, microbiology, virology, and geomicrobiology. However, HIM is not just an imaging technique. The ability to use the instrument for milling biological objects as small as viruses offers unique opportunities which are not possible with more conventional focused ion beams, such as gallium. Several pioneering technical developments, such as methods to couple secondary ion mass spectrometry (SIMS) or ionoluminescence with the HIM, also offer the possibility for new and exciting research on biological materials. In this review, we present a comprehensive overview of almost all currently published literature which has demonstrated the application of HIM for imaging of biological specimens. We also discuss some technical features of this unique type of instrument and highlight some of the new advances which will likely become more widely used in the years to come.

Biochar (BC) and magnetite (Fe3O4) nanoparticles (MNP) have both received considerable recent attention in part due to their potential use in water treatment. While both are effective independently in the removal of a range of anionic metals from aqueous solution, the efficacy of these materials is reduced considerably at neutral pH due to decreased metal adsorption and MNP aggregation. In addition to synthetic metal oxide–biochar composites for use in treatment and remediation technologies, aggregates may also occur in nature when pyrolytic carbon is deposited in soils. In this study, we tested whether magnetite synthesized in the presence of biochar leads to increased removal efficiency of hexavalent chromium, Cr(VI), at the mildly acidic to neutral pH values characteristic of most natural and contaminated aqueous environments. To do so, magnetite nanoparticles and biochar produced from ground willow were synthesized to form composites (MNP–BC). Batch studies showed that MNP–BC markedly enhanced both adsorption and reduction of Cr(VI) from aqueous solution at acidic to neutral pH as compared to MNP and BC separately, suggesting a strong synergetic effect of hybridizing Fe3O4 with BC. Mechanistically, the Cr(VI) removal processes occurred through both adsorption and intraparticle diffusion followed by reduction to Cr(III). Synchrotron-based X-ray absorption spectroscopy analyses confirmed that Cr(VI) was reduced at the surface of MNP–BC, with electrons derived directly from both biochar and magnetite at low pH, while at near-neutral pH, biochar increased Cr(VI) reduction by inhibiting MNP aggregation. Extended X-ray absorption fine structure fitting results confirmed that the Cr(III) precipitates consist of Cr(OH)3 and chromite (Cr2FeO4) nanoparticles. Our results demonstrate that MNP–BC composites have great potential as a material for the treatment of chromate-containing aqueous solutions across a wide range of pH values, and provide information valuable broadly relevant to soils and sediments that contain biochar.

This article highlights intra-regional variation in the extent of the COVID-19 outbreaks in South America generally and then provides an assessment of the nature and extent of outbreaks in South Am...

This article documents the extent of COVID-19 outbreaks in the North American, Central American, and Caribbean regions, and then compares the country-specific COVID-19 mitigation strategies impleme...

We review the nature and extent of COVID-19 outbreaks across corrections systems globally, and document the types of front-end, in-prison, and back-end mitigation strategies used to address the COV...

Anaerobic nitrate-dependent Fe(II) oxidation (NDFeO) is widespread in various aquatic environments and plays a major role in iron and nitrogen redox dynamics. However, evidence for truly enzymatic, autotrophic NDFeO remains limited, with alternative explanations involving the coupling of heterotrophic denitrification with the abiotic oxidation of structurally bound or aqueous Fe(II) by reactive intermediate nitrogen (N) species (chemodenitrification). The extent to which chemodenitrification is caused (or enhanced) by ex vivo surface catalytic effects has not been directly tested to date. To determine whether the presence of either an Fe(II)-bearing mineral or dead biomass (DB) catalyses chemodenitrification, two different sets of anoxic batch experiments were conducted: 2 mM Fe(II) was added to a low-phosphate medium, resulting in the precipitation of vivianite (Fe3(PO4)2), to which 2 mM nitrite (NO2-) was later added, with or without an autoclaved cell suspension (∼1.96×108 cells mL−1) of Shewanella oneidensis MR-1. Concentrations of nitrite (NO2-), nitrous oxide (N2O), and iron (Fe2+, Fetot) were monitored over time in both set-ups to assess the impact of Fe(II) minerals and/or DB as catalysts of chemodenitrification. In addition, the natural-abundance isotope ratios of NO2- and N2O (δ15N and δ18O) were analysed to constrain the associated isotope effects. Up to 90 % of the Fe(II) was oxidized in the presence of DB, whereas only ∼65 % of the Fe(II) was oxidized under mineral-only conditions, suggesting an overall lower reactivity of the mineral-only set-up. Similarly, the average NO2- reduction rate in the mineral-only experiments (0.004±0.003 mmol L−1 d−1) was much lower than in the experiments with both mineral and DB (0.053±0.013 mmol L−1 d−1), as was N2O production (204.02±60.29 nmol L−1 d−1). The N2O yield per mole NO2- reduced was higher in the mineral-only set-ups (4 %) than in the experiments with DB (1 %), suggesting the catalysis-dependent differential formation of NO. N-NO2- isotope ratio measurements indicated a clear difference between both experimental conditions: in contrast to the marked 15N isotope enrichment during active NO2- reduction (15εNO2=+10.3 ‰) observed in the presence of DB, NO2- loss in the mineral-only experiments exhibited only a small N isotope effect (<+1 ‰). The NO2--O isotope effect was very low in both set-ups (18εNO2 <1 ‰), which was most likely due to substantial O isotope exchange with ambient water. Moreover, under low-turnover conditions (i.e. in the mineral-only experiments as well as initially in experiments with DB), the observed NO2- isotope systematics suggest, transiently, a small inverse isotope effect (i.e. decreasing NO2- δ15N and δ18O with decreasing concentrations), which was possibly related to transitory surface complexation mechanisms. Site preference (SP) of the 15N isotopes in the linear N2O molecule for both set-ups ranged between 0 ‰ and 14 ‰, which was notably lower than the values previously reported for chemodenitrification. Our results imply that chemodenitrification is dependent on the available reactive surfaces and that the NO2- (rather than the N2O) isotope signatures may be useful for distinguishing between chemodenitrification catalysed by minerals, chemodenitrification catalysed by dead microbial biomass, and possibly true enzymatic NDFeO.

SUMMARY Low-temperature oxidation (LTO) of magnetite is an alteration process which occurs under normal atmospheric conditions, causing maghemitization. The use of magnetic properties as palaeoclimate proxies requires improved understanding of how humidity and temperature affect such processes. We exposed natural magnetite, with grain size ranging from 90 per cent at 70 °C showed the strongest degree of LTO with an increase of the oxidation degree by ∼3 per cent according to Tv, and it was the only setup where partial alteration to hematite was indicated by Mössbauer analysis. The sample with extremely dry conditions (rH of ∼5 per cent) at 70 °C, and the sample that was exposed to cycles of high and low humidity in 2-weeks alternation at 70 °C, both revealed a smaller degree of LTO. The smallest change of the high temperature setups was observed for the sample with intermediate rH of ∼13 per cent. The results suggest a non-linear sensitivity of magnetite alteration to humidity conditions, high humidity strongly favours alteration, but alteration is strongly reduced when extreme humidity alternates with dry conditions, suggesting an importance of seasonality in natural weathering.

Human-induced climate change through the over liberation of greenhouse gases, resulting in devastating consequences to the environment, is a concern of considerable global significance which has fu...

Natural organic matter (NOM) is known to affect the microbial reduction and transformation of ferrihydrite, but its implication toward cadmium (Cd) associated with ferrihydrite is not well-known. Here, we investigated how Cd is redistributed when ferrihydrite undergoes microbial reduction in the presence of NOM. Incubation with Geobacter sulfurreducens showed that both the rate and the extent of reduction of Cd-loaded ferrihydrite were enhanced by increasing concentrations of NOM (i.e., C/Fe ratio). Without NOM, only 3-4% of Fe(III) was reduced, but around 61% of preadsorbed Cd was released into solution due to ferrihydrite transformation to lepidocrocite. At high C/Fe ratio (1.6), more than 35% of Fe(III) was reduced, as NOM can facilitate bioreduction by working as an electron shuttle and decreased aggregate size, but only a negligible amount of Cd was released into solution, thus decreasing Cd toxicity and prolonging microbial Fe(III) reduction. No ferrihydrite transformation was observed at high C/Fe ratios using Mossbauer spectroscopy and X-ray diffraction, and X-ray absorption spectroscopy indicated the proportion of Cd-OM bond increased after microbial reduction. This study shows that the presence of NOM leads to less mobilization of Cd under reducing condition possibly by inhibiting ferrihydrite transformation and recapturing Cd through Cd-OM bond.

Biogenic nanoscale vanadium magnetite is produced by converting V(V)-bearing ferrihydrites through reductive transformation using the metal-reducing bacterium Geobacter sulfurreducens. With increasing vanadium in the ferrihydrite, the amount of V-doped magnetite produced decreased due to V-toxicity which interrupted the reduction pathway ferrihydrite–magnetite, resulting in siderite or goethite formation. Fe L2,3 and V L2,3 X-ray absorption spectra and data from X-ray magnetic circular dichroism analysis revealed the magnetite to contain the V in the Fe(III) Oh site, predominately as V(III) but always with a component of V(VI), present a consistent V(IV)/V(III) ratio in the range 0.28 to 0.33. The bacteriogenic production of V-doped magnetite nanoparticles from V-doped ferrihydrite is confirmed and the work reveals that microbial reduction of contaminant V(V) to V(III)/V(IV) in the environment will occur below the Fe-redox boundary where it will be immobilised in biomagnetite nanoparticles.

Uranium (U) in situ bioremediation has been investigated as a cost-effective strategy to tackle U contamination in the subsurface. While uraninite was believed to be the only product of bioreduction, numerous studies have revealed that noncrystalline U(IV) species (NCU(IV)) are dominant. This finding brings into question the effectiveness of bioremediation because NCU(IV) species are expected to be labile and susceptible to oxidation. Thus, understanding the stability of NCU(IV) in the environment is of crucial importance. Fe(II) minerals (such as FeS) are often associated with U(IV) in bioremediated or naturally reduced sediments. Their impact on the stability of NCU(IV) is not well understood. Here, we show that, at high dissolved oxygen concentrations, FeS accelerates NCU(IV) reoxidation. We hypothesize that either highly reactive ferric minerals or radical S species produced by the oxidation of FeS drive this rapid reoxidation of NCU(IV). Furthermore, we found evidence for the contribution of reactive oxygen species to NCU(IV) reoxidation. This work refines our understanding of the role of iron sulfide minerals in the stability of tetravalent uranium in the presence of oxygen in a field setting such as contaminated sites or uranium-bearing naturally reduced zones.

Weathering is a fundamental process that controls the development of Earth's surface by the formation of erodible material and the release of mineral-bound nutrients. Weathering at depth has been predominantly studied in humid environments, where fluid flow sets mineralogical transformations, whereas (semi-)arid regions were barely investigated in this respect. In many studies the weathering of iron-bearing minerals was shown to play a major role for the advance of weathering at depth. Weathering of iron-bearing minerals is often superimposed on factors that precondition rocks for weathering such as hydrothermal alteration and fracturing by tectonic stress. The low degree of water-rock interactions in (semi-)arid climates offers the opportunity to single out the preconditioning factors and explore the role of iron-bearing minerals for weathering in detail. To this end the interactions of tectonic fracturing, hydrothermal alteration and weathering were investigated in a deep, weakly weathered profile of plutonic rock in a semi-arid region (Santa Gracia, Northern Chile). The profile was recovered by an 87-m-deep drill core and a 2-m-deep soil pit which were used to investigate the mineral composition, magnetic susceptibility, geochemical gradients, and Fe redox-state. Non-cemented fractures of tectonic origin were identified as pathways for the transport of fluids and reagents to depth that are fuelling the initial weathering reactions. Previous hydrothermal fluids mainly migrated along the same fractures and altered the properties of the original bedrock. Therefore, the weathering features along fractures depend on the preconditioning by hydrothermal alteration and tectonic stress which affected the vicinity of these fractures. From the fracture surfaces, water and O2 diffuse into the rock and initiate oxidation and dissolution-reprecipitation reactions. Our study shows that the transformation of iron-bearing silicates (especially biotite) to Fe(III) (oxyhydr)oxides and clay minerals is the dominant weathering-promoting process as it produces stress which leads to micro-fracturing of the rock and finally to the formation of saprolite. Deciphering the links between tectonic fracturing, hydrothermal alteration, and weathering-induced fracturing by iron-bearing silicates in semi-arid settings provides unique insights into the controls of deep weathering in regions with limited fluid flow.

International audience; There is longstanding controversy about the genesis of magnetite in banded iron formations (BIFs), particularly concerning whether it is of abiogenic or biogenic origin. The composition of trace elements within magnetite produced by magnetotactic bacteria has been proposed as a promising marker for its biological origin; however further experimental evidence is required to investigate whether this also holds true for iron-metabolizing bacteria. Here, we compared the behavior of zinc (Zn) and nickel (Ni) in magnetite produced either abiogenically (ferrihydrite reacting with dissolved Fe2+) or biogenically (ferrihydrite reacting with dissolved Fe2+ generated via the dissimilatory iron-reducing bacterium - DIRB - Shewanella oneidensis MR-1). These abiotic and biotic incubations were applied for transforming three ferrihydrite (Fh) substrates: (1) Control Fh without added trace elements; (2) Zn-coprecipitated ferrihydrite (ZnFh); and (3) Ni-coprecipitated ferrihydrite (NiFh) in both NaHCO3 and HEPES buffer. X-ray diffraction revealed magnetite as the dominant transformation product for all reaction conditions, while siderite was only detected in experiments containing NaHCO3 as buffer. Based on similar initial dissolved Ni and Zn concentrations, we found opposing behavior of Zn and Ni where Zn showed enrichment in abiogenic magnetite, while Ni was more enriched in biogenic magnetite. Combining supposed Zn and Ni concentrations in Precambrian seawater and magnetite mineral grains from three formations deposited at different ages (i.e. 3.75 Ga Nuvvuagittuq Supracrustal Belt, 2.45 Ga Weeli Wolli Iron Formation, and 1.88 Ga Sokoman Iron Formation), we reconstructed potential Zn and Ni partition coefficients between Precambrian seawater and magnetite minerals. The reconstructed potential Zn and Ni partition coefficients suggested that these magnetite minerals from three formations were abiogenic. These differing behaviors suggest the possibility of using Zn and Ni partition coefficient ratios as a means of determining the presence or absence of DIRB in the formation of ancient magnetite deposits.

Cadmium (Cd) adversely affects human health by entering the food chain via anthropogenic activity. In order to mitigate risk, a better understanding of the biogeochemical mechanisms limiting Cd mobility in the environment is needed. While Cd is not redox-active, Cd speciation varies (i.e., aqueous, complexed, adsorbed), and influences mobility. Here, the cycling of Cd in relation to initial speciation during the growth of Geobacter sulfurreducens was studied. Either fumarate or ferrihydrite (Fh) was provided as an electron acceptor and Cd was present as: (1) an aqueous cation, (2) an aqueous complex with cysteine, which is often present in metal stressed soil environments, or (3) adsorbed to Fh. During microbial Fe(III) reduction, the removal of Cd was substantial (∼80% removal), despite extensive Fe(II) production (ratio Fe(II)total : Fetotal = 0.8). When fumarate was the electron acceptor, there was higher removal from solution when Cd was complexed with cysteine (97–100% removal) compared to aqueous Cd (34–50%) removal. Confocal laser scanning microscopy (CLSM) demonstrated the formation of exopolymeric substances (EPS) in all conditions and that Cd was correlated with EPS in the absence of Fe minerals (r = 0.51–0.56). Most notable is that aqueous Cd was more strongly correlated with Geobacter cells (r = 0.72) compared to Cd–cysteine complexes (r = 0.51). This work demonstrates that Cd interactions with cell surfaces and EPS, and Cd solubility during metabolic activity are dependent upon initial speciation. These processes may be especially important in soil environments where sulfur is limited and Fe and organic carbon are abundant.

Nitrate removal in oligotrophic environments is often limited by the availability of suitable organic electron donors. Chemolithoautotrophic bacteria may play a key role in denitrification in aquifers depleted in organic carbon. Under anoxic and circumneutral pH conditions, iron(II) was hypothesized to serve as an electron donor for microbially mediated nitrate reduction by Fe(II)-oxidizing (NRFeOx) microorganisms. However, lithoautotrophic NRFeOx cultures have never been enriched from any aquifer, and as such, there are no model cultures available to study the physiology and geochemistry of this potentially environmentally relevant process. Using iron(II) as an electron donor, we enriched a lithoautotrophic NRFeOx culture from nitrate-containing groundwater of a pyrite-rich limestone aquifer. In the enriched NRFeOx culture that does not require additional organic cosubstrates for growth, within 7 to 11 days, 0.3 to 0.5 mM nitrate was reduced and 1.3 to 2 mM iron(II) was oxidized, leading to a stoichiometric NO(3)(−)/Fe(II) ratio of 0.2, with N(2) and N(2)O identified as the main nitrate reduction products. Short-range ordered Fe(III) (oxyhydr)oxides were the product of iron(II) oxidation. Microorganisms were observed to be closely associated with formed minerals, but only few cells were encrusted, suggesting that most of the bacteria were able to avoid mineral precipitation at their surface. Analysis of the microbial community by long-read 16S rRNA gene sequencing revealed that the culture is dominated by members of the Gallionellaceae family that are known as autotrophic, neutrophilic, and microaerophilic iron(II) oxidizers. In summary, our study suggests that NRFeOx mediated by lithoautotrophic bacteria can lead to nitrate removal in anthropogenically affected aquifers. IMPORTANCE Removal of nitrate by microbial denitrification in groundwater is often limited by low concentrations of organic carbon. In these carbon-poor ecosystems, nitrate-reducing bacteria that can use inorganic compounds such as Fe(II) (NRFeOx) as electron donors could play a major role in nitrate removal. However, no lithoautotrophic NRFeOx culture has been successfully isolated or enriched from this type of environment, and as such, there are no model cultures available to study the rate-limiting factors of this potentially important process. Here, we present the physiology and microbial community composition of a novel lithoautotrophic NRFeOx culture enriched from a fractured aquifer in southern Germany. The culture is dominated by a putative Fe(II) oxidizer affiliated with the Gallionellaceae family and performs nitrate reduction coupled to Fe(II) oxidation leading to N(2)O and N(2) formation without the addition of organic substrates. Our analyses demonstrate that lithoautotrophic NRFeOx can potentially lead to nitrate removal in nitrate-contaminated aquifers.

Microbial reduction of Fe(III) minerals is a prominent process in redoximorphic soils and is strongly affected by organic matter (OM). We herein determined the rate and extent of microbial reduction of ferrihydrite (Fh) with either adsorbed or coprecipitated OM by Geobacter sulfurreducens. We focused on OM-mediated effects on electron uptake and alterations in Fh crystallinity. The OM was obtained from anoxic soil columns (effluent OM, efOM) and included-unlike water-extractable OM-compounds released by microbial activity under anoxic conditions. We found that organic molecules in efOM had generally no or only very low electron-accepting capacity and were incorporated into the Fh aggregates when coprecipitated with Fh. Compared to OM-free Fh, adsorption of efOM to Fh decelerated the microbial Fe(III) reduction by passivating the Fh surface toward electron uptake. In contrast, coprecipitation of Fh with efOM accelerated the microbial reduction, likely because efOM disrupted the Fh structure, as noted by Mossbauer spectroscopy. Additionally, the adsorbed and coprecipitated efOM resulted in a more sustained Fe(III) reduction, potentially because efOM could have effectively scavenged biogenic Fe(II) and prevented the passivation of the Fh surface by the adsorbed Fe(II). Fe(III)-OM coprecipitates forming at anoxic-oxic interfaces are thus likely readily reducible by Fe(III)-reducing bacteria in redoximorphic soils.

Neutrophilic microbial pyrite (FeS2) oxidation coupled to denitrification is thought to be an important natural nitrate attenuation pathway in nitrate-contaminated aquifers. However, the poor solubility of pyrite raises questions about its bioavailability and the mechanisms underlying its oxidation. Here, we investigated direct microbial pyrite oxidation by a neutrophilic chemolithoautotrophic nitrate-reducing Fe(II)-oxidizing culture enriched from a pyrite-rich aquifer. We used pyrite with natural abundance (NA) of Fe isotopes (NAFe-pyrite) and 57Fe-labeled siderite to evaluate whether the oxidation of the more soluble Fe(II)-carbonate (FeCO3) can indirectly drive abiotic pyrite oxidation. Our results showed that in setups where only pyrite was incubated with bacteria, direct microbial pyrite oxidation contributed ca. 26% to overall nitrate reduction. The rest was attributed to the oxidation of elemental sulfur (S0), present as a residue from pyrite synthesis. Pyrite oxidation was evidenced in the NAFe-pyrite/57Fe-siderite setups by maps of 56FeO and 32S obtained using a combination of SEM with nanoscale secondary ion MS (NanoSIMS), which showed the presence of 56Fe(III) (oxyhydr)oxides that could solely originate from 56FeS2. Based on the fit of a reaction model to the geochemical data and the Fe-isotope distributions from NanoSIMS, we conclude that anaerobic oxidation of pyrite by our neutrophilic enrichment culture was mainly driven by direct enzymatic activity of the cells. The contribution of abiotic pyrite oxidation by Fe3+ appeared to be negligible in our experimental setup.

STUDY QUESTION Do genetic variations in the DNA damage response pathway modify the adverse effect of alkylating agents on ovarian function in female childhood cancer survivors (CCS)? SUMMARY ANSWER Female CCS carrying a common BR serine/threonine kinase 1 (BRSK1) gene variant appear to be at 2.5-fold increased odds of reduced ovarian function after treatment with high doses of alkylating chemotherapy. WHAT IS KNOWN ALREADY Female CCS show large inter-individual variability in the impact of DNA-damaging alkylating chemotherapy, given as treatment of childhood cancer, on adult ovarian function. Genetic variants in DNA repair genes affecting ovarian function might explain this variability. STUDY DESIGN, SIZE, DURATION CCS for the discovery cohort were identified from the Dutch Childhood Oncology Group (DCOG) LATER VEVO-study, a multi-centre retrospective cohort study evaluating fertility, ovarian reserve and risk of premature menopause among adult female 5-year survivors of childhood cancer. Female 5-year CCS, diagnosed with cancer and treated with chemotherapy before the age of 25 years, and aged 18 years or older at time of study were enrolled in the current study. Results from the discovery Dutch DCOG-LATER VEVO cohort (n = 285) were validated in the pan-European PanCareLIFE (n = 465) and the USA-based St. Jude Lifetime Cohort (n = 391). PARTICIPANTS/MATERIALS, SETTING, METHODS To evaluate ovarian function, anti-Müllerian hormone (AMH) levels were assessed in both the discovery cohort and the replication cohorts. Using additive genetic models in linear and logistic regression, five genetic variants involved in DNA damage response were analysed in relation to cyclophosphamide equivalent dose (CED) score and their impact on ovarian function. Results were then examined using fixed-effect meta-analysis. MAIN RESULTS AND THE ROLE OF CHANCE Meta-analysis across the three independent cohorts showed a significant interaction effect (P = 3.0 × 10−4) between rs11668344 of BRSK1 (allele frequency = 0.34) among CCS treated with high-dose alkylating agents (CED score ≥8000 mg/m2), resulting in a 2.5-fold increased odds of a reduced ovarian function (lowest AMH tertile) for CCS carrying one G allele compared to CCS without this allele (odds ratio genotype AA: 2.01 vs AG: 5.00). LIMITATIONS, REASONS FOR CAUTION While low AMH levels can also identify poor responders in assisted reproductive technology, it needs to be emphasized that AMH remains a surrogate marker of ovarian function. WIDER IMPLICATIONS OF THE FINDINGS Further research, validating our findings and identifying additional risk-contributing genetic variants, may enable individualized counselling regarding treatment-related risks and necessity of fertility preservation procedures in girls with cancer. STUDY FUNDING/COMPETING INTEREST(S) This work was supported by the PanCareLIFE project that has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement no 602030. In addition, the DCOG-LATER VEVO study was funded by the Dutch Cancer Society (Grant no. VU 2006-3622) and by the Children Cancer Free Foundation (Project no. 20) and the St Jude Lifetime cohort study by NCI U01 CA195547. The authors declare no competing interests. TRIAL REGISTRATION NUMBER N/A.