Musculoskeletal disorders and age-related musculoskeletal decline are major contributors to the burden of ill health seen in older subjects. Despite this increased burden, these chronic disorders of old age receive a relatively small proportion of national research funds. Much has been learned about fundamental processes involved in ageing from basic science research and this is leading to identification of key pathways that mediate ageing which may help the search for interventions to reduce age-related musculoskeletal decline. This short review will focus on the role of reactive oxygen species in age-related skeletal muscle decline and on the implications of this work for potential nutritional interventions in sarcopenia. The key physiological role of reactive oxygen species is now known to be in mediating redox signalling in muscle and other tissues and ageing leads to disruption of such pathways. In muscle, this is reflected in an age-related attenuation of specific adaptations and responses to contractile activity that impacts the ability of skeletal muscle from ageing individuals to respond to exercise. These pathways provides potential targets for identification of logical interventions that may help maintain muscle mass and function during ageing.

Geologic repositories for spent nuclear fuel use bentonite as a buffer to protect the metallic containers confining the radioactive material. Sulfate-reducing bacteria, which may be present in groundwater, at the bentonite–host rock interface or eventually within the bentonite may produce sulfide, representing a potential threat for the metallic canisters, particularly copper. Bentonites can act as potential sulfide scavengers. Little is yet known, however, regarding the underlying mechanisms, the maximum extent of sulfide consumption, and the potential impacts on bentonite structure under repository conditions. In the current study, concentrated (4–150 mM) sulfide solutions were reacted in batch experiments with six natural Fe-bearing bentonites, with various purified Fe-bearing components of bentonite (a series of purified montmorillonites and three iron (oxyhydr)oxides), and with one synthetic mixture, for up to 1.5 months at pH values ranging from 7 to 13. The solutions were analyzed by colorimetry to determine sulfide and polysulfide concentrations and the solids were analyzed by 57Fe Mössbauer spectrometry to determine iron speciation. Important sulfide consumption coupled with a reduction of structural Fe in the clay samples was observed. Not all clay structural Fe was reactive toward sulfide; the proportion of active structural Fe depended on the clay structure and pH. In the presence of excess sulfide in solution regarding Fe in the solid sample, the clay structural Fe was found to be the main reactant while the reaction with iron (oxyhydr)oxides was largely inhibited. Three bentonite groups were distinguished, based on the sulfide oxidation capacity of their main clayey component.

Excavated bentonite from two large iron-bentonite field experiments at Äspö Hard Rock Laboratory in Sweden was investigated with respect to iron redox chemistry and mineralogy. The iron redox chemistry was studied by Fe K-edge X-ray absorption near edge structure spectroscopy and the mineral phases were studied using X-ray diffraction. Bentonite is to be used as a buffer material in high-level radioactive waste repositories to protect the waste containers from their surroundings. Montmorillonite, which is responsible for the sealing properties in the bentonite, is susceptible to redox reactions. A change in the montmorillonite iron redox chemistry may affect its layer charge and hence its properties. The experiments included are the first Alternative Buffer Material test (ABM1) and the Temperature Buffer Test (TBT). The clays were heated to a maximum of ~130°C (ABM1) or ~150°C (TBT) for 2.5 and 7 y, respectively. In the central part of the compacted clay blocks was placed an iron heater and the distance from the heater to the rock was ~10 cm (ABM1) and ~50 cm (TBT), respectively. Eleven different clay materials were included in the ABM1 experiment and five were analyzed here. In the ABM1 experiment, the Fe(II)/Fe(III) ratio was increased in several samples from the vicinity of the heater. Kinetic data were collected and showed that most of the Fe(II)-rich samples oxidized rapidly when exposed to atmospheric oxygen. In the TBT experiment the corrosion products were dominated by Fe(III) and no significant increase in Fe(II) was seen. In ABM1, reducing conditions were achieved, at least in parts of the experiment; in TBT, reducing conditions were not achieved. The difference was attributed to the larger scale of the TBT experiment, providing more oxygen after the installation, and to the longer time taken for water saturation; oxidation of the samples during excavation cannot be ruled out. Minor changes in the bentonite mineral phases were found in some cases where direct contact was made with the iron heater but no significant impact on the bentonite performance in high-level radioactive waste applications was expected as a result.

Nitrate is linked to chronic human illness and to a variety of environmental problems, and continues to be a contaminant of concern in soils and natural waters. Improved methods for nitrate abatement, thus, are still needed. The purpose of this study was to assess the potential for redox-modified, iron-bearing clay minerals to act as nitrate decontamination agents in natural environments. The model clay mineral tested was ferruginous smectite (sample SWa-1) exchanged with either sodium (Na+) or polydiallyldimethylammonium chloride (poly-DADMAC). Structural iron (Fe) in SWa-1 was in either the oxidized or reduced state. Little nitrate uptake was observed in the Na+-SWa-1, which was attributed to coulombic repulsion between the basal surfaces of the smectite and the nitrate anion. The addition of the DADMAC to the SWa-1 reversed the electrostatic charge manifested at the smectite surface from negative to positive, as measured by the zeta (ζ) potential. The positively charged poly-DADMAC-SWa-1 yielded high nitrate uptake due to coulombic attraction in both the oxidized and reduced states of the Fe in the SWa-1. The presence of reduced structural Fe(II) in the positively charged poly-DADMAC-SWa-1 enabled a chemical reduction reaction with the nitrate to produce nitrite. The amounts of nitrite found in solution, however, failed to account for all of the Fe(II) oxidized, so other N reduction products may also have formed or perhaps nitrite was also present in the adsorbed phase. The effects of other complexities, such as polymer configuration at the surface, also need further investigation. The results do clearly establish abiotic nitrate reduction to nitrite and possibly other reduction products. The combination of bacterial activity in soils and sediments, which is known to reduce structural Fe in smectites, and the abundance of organic cations in soil organic matter creates an environment where reversed-charge smectite could exist in nature. This represents a potentially effective system for mitigating harmful effects of nitrate in soils, sediments, groundwater, and surface water.

The reduction of structural Fe in smectite is mediated either abiotically, by reaction with dithionite, or biotically, by Fe-reducing bacteria. The effects of abiotic reduction on clay-surface chemistry are much better known than the effects of biotic reduction. Since bacteria are probably the principal agent for mediating redox processes in natural soils and sediments, further study is needed to ascertain the differences between biotic and abiotic reduction processes. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in smectites on the clay structure as observed by infrared spectroscopy. Three reference smectites, namely, Garfield nontronite, ferruginous smectite (SWa-1), and Upton, Wyoming, montmorillonite, were reduced to similar levels by either Shewanella oneidensis or by pH-buffered sodium dithionite. Each sample was then analyzed by Fourier transform infrared spectroscopy (FTIR). Parallel samples were reoxidized by bubbling O2 gas through the reduced suspension at room temperature prior to FTIR analysis. Redox states were quantified by chemical analysis, using 1, 10-phenanthroline. The reduction level achieved by dithionite was controlled to approximate that of the bacterial reduction treatment so that valid comparisons could be made between the two treatments. Bacterial reduction was achieved by incubating the Na-saturated smectites with S. oneidensis strain MR-1 in a minimal medium including 20 mM lactate. After redox treatment, the clay was washed four times with deoxygenated 5 mM NaCl. The sample was then prepared either as a self-supporting film for OH-stretching and deformation bands or as a deposit on ZnSe windows for Si-O stretching bands and placed inside a controlled atmosphere cell also fitted with ZnSe windows. The spectra from bacteria-treated samples were compared with dithionite-treated samples having a similar Fe(II) content. The changes observed in all three spectral regions (OH stretching, M2-O-H deformation, and Si-O stretching) for bacteria-reduced smectite were similar to results obtained at a comparable level of reduction by dithionite. In general, the shift of the structural OH vibration and the Si-O vibration, and the loss of intensity of OH groups, indicate that the bonding and/or symmetry properties in the octahedral and tetrahedral sheets changes as Fe(III) reduces to Fe(II). Upon reoxidation, peak positions and intensities of the reduced smectites were largely restored to the unaltered condition with some minor exceptions. These observations are interpreted to mean that bacterial reduction of Fe modifies the crystal structures of Fe-bearing smectites, but the overall effects are modest and of about the same extent as dithionite at similar levels of reduction. No extensive changes in clay structure were observed under conditions present in our model system.

Se deficiency causes impaired growth of fish skeletal muscle due to the retarded hypertrophy of muscle fibres. However, the inner mechanisms remain unclear. According to our previous researches, we infer this phenomenon is associated with Se deficiency-induced high concentration of reactive oxygen species (ROS), which could suppress the target of rapamycin complex 1 (TORC1) pathway-mediated protein synthesis by inhibiting protein kinase B (Akt), an upstream protein of TORC1. To test this hypothesis, juvenile zebrafish (45 d post-fertilisation) were fed a basal Se-adequate diet or a basal Se-deficient diet or them supplemented with an antioxidant (DL-α-tocopherol acetate, designed as VE) or a TOR activator (MHY1485) for 30 d. Zebrafish fed Se-deficient diets exhibited a clear Se-deficient status in skeletal muscle, which was not influenced by dietary VE and MHY1485. Se deficiency significantly elevated ROS concentrations, inhibited Akt activity and TORC1 pathway, suppressed protein synthesis in skeletal muscle, and impaired hypertrophy of skeletal muscle fibres. However, these negative effects of Se deficiency were partly (except that on ROS concentration) alleviated by dietary MHY1485 and completely alleviated by dietary VE. These data strongly support our speculation that Se deficiency-induced high concentration of ROS exerts a clear inhibiting effect on TORC1 pathway-mediated protein synthesis by regulating Akt activity, thereby restricting the hypertrophy of skeletal muscle fibres in fish. Our findings provide a mechanistic explanation for Se deficiency-caused retardation of fish skeletal muscle growth, contributing to a better understanding of the nutritional necessity and regulatory mechanisms of Se in fish muscle physiology.

Remnants of some of the planet’s most ancient life forms, stromatolites in the late Mesoproterozoic sea of the Chattisgarh Basin, India, preserve a conspicuous sinuous pattern. They occur as successive biostromes, 10–30 cm thick, separated by 2–5-cm-thick marly layers and discrete bioherms up to several metres thick and 20 m across. Stromatolite columns in the Chandi Formation are 5–10 cm high, sinuous, inclined and straight, with both branched and non-branched types. These stromatolites are composed of calcite micrite and show well defined light and dark laminae with evidence of erosion between lamina sets. The column sinuosity probably originated as a response to changes in direction and strength of currents. Successive flat beds of stromatolite (biostromes), separated by marl/clay horizons, impart a rhythmic pattern to the succession. The Chandi sinuous stromatolite columns resemble those occurring in China, North America and Siberia, of a comparable age, suggesting that similar marine conditions of stromatolite formation might have been operating in the late Mesoproterozoic seas worldwide. However, the petrographic and sedimentological analyses of these stromatolites indicate their development through in situ production of carbonate with some trapping and binding of detrital sediment. As a result of the presence of terrigenous material within the stromatolites, whole-rock geochemical analyses for trace elements and rare earth elements cannot be used for interpretation of seawater chemistry and the redox conditions at the time.

Previous work led to the proposal that the precision feeding of a high-concentrate diet may represent a potential method with which to enhance feed efficiency (FE) when rearing dairy heifers. However, the physiological and metabolic mechanisms underlying this approach remain unclear. This study used metabolomics analysis to investigate the changes in plasma metabolites of heifers precision-fed diets containing a wide range of forage to concentrate ratios. Twenty-four half-sib Holstein heifers, with a similar body condition, were randomly assigned into four groups and precision fed with diets containing different proportions of concentrate (20%, 40%, 60% and 80% based on DM). After 28 days of feeding, blood samples were collected 6 h after morning feeding and gas chromatography time-of-flight/MS was used to analyze the plasma samples. Parameters of oxidative status were also determined in the plasma. The FE (after being corrected for gut fill) increased linearly (P < 0.01) with increasing level of dietary concentrate. Significant changes were identified for 38 different metabolites in the plasma of heifers fed different dietary forage to concentrate ratios. The main pathways showing alterations were clustered into those relating to carbohydrate and amino acid metabolism; all of which have been previously associated with FE changes in ruminants. Heifers fed with a high-concentrate diet had higher (P < 0.01) plasma total antioxidant capacity and superoxide dismutase but lower (P ≤ 0.02) hydroxyl radical and hydrogen peroxide than heifers fed with a low-concentrate diet, which might indicate a lower plasma oxidative status in the heifers fed a high-concentrate diet. Thus, heifers fed with a high-concentrate diet had higher FE and antioxidant capacity but a lower plasma oxidative status as well as changed carbohydrate and amino acid metabolism. Our findings provide a better understanding of how forage to concentrate ratios affect FE and metabolism in the precision-fed growing heifers.

Sulfur-bearing monazite-(Ce) occurs in silicified carbonatite at Eureka, Namibia, forming rims up to ~0.5 mm thick on earlier-formed monazite-(Ce) megacrysts. We present X-ray photoelectron spectroscopy data demonstrating that sulfur is accommodated predominantly in monazite-(Ce) as sulfate, via a clino-anhydrite-type coupled substitution mechanism. Minor sulfide and sulfite peaks in the X-ray photoelectron spectra, however, also indicate that more complex substitution mechanisms incorporating S2– and S4+ are possible. Incorporation of S6+ through clino-anhydrite-type substitution results in an excess of M2+ cations, which previous workers have suggested is accommodated by auxiliary substitution of OH– for O2–. However, Raman data show no indication of OH–, and instead we suggest charge imbalance is accommodated through F– substituting for O2–. The accommodation of S in the monazite-(Ce) results in considerable structural distortion that may account for relatively high contents of ions with radii beyond those normally found in monazite-(Ce), such as the heavy rare earth elements, Mo, Zr and V. In contrast to S-bearing monazite-(Ce) in other carbonatites, S-bearing monazite-(Ce) at Eureka formed via a dissolution–precipitation mechanism during prolonged weathering, with S derived from an aeolian source. While large S-bearing monazite-(Ce) grains are likely to be rare in the geological record, formation of secondary S-bearing monazite-(Ce) in these conditions may be a feasible mineral for dating palaeo-weathering horizons.

Mineralogical, bulk and field leachate compositions are used to identify important processes governing the evolution of discharges from a coal spoil heap in County Durham. These processes are incorporated into a numerical one-dimensional advective-kinetic reactive transport model which reproduces field results, including gas compositions, to within an order of magnitude. Variation of input parameters allows the effects of incorrect initial assumptions on elemental profiles and discharge chemistry to be assessed. Analytical expressions for widths and speeds of kinetic reaction fronts are developed and used to predict long-term development of mineralogical distribution within the heap. Results are consistent with observations from the field site. Pyrite oxidation is expected to dominate O2 consumption in spoil heaps on the decadal timescale, although C oxidation may stabilize contaminants in effluents on the centennial scale.

The water column chemistry of lake St Eloy (St Eloy-les Mines, Allier, France) was monitored over a period of a year. This is a small stratified lake created by subsidence of an underground coal mine. The results show a permanent stratification and the development of two water bodies with contrasting chemistry. The superficial oxic layer (i.e. the upper 5 m) is of high water quality and the water, not affected by seasonal changes, is suitable as a source of drinking water. In contrast, the deeper layer is permanently anoxic and the waters have a conductivity which is six times greater than in the epilimnion. Due to density difference and the small size of the lake, no turn-over occurs and all elements that diffuse from bottom sediments are strongly concentrated in the hypolimnion. Arsenic concentrations are very low in the epilimnion, but they increase quickly with depth below the oxycline, to reach up to 7 μm below 8 m depth. Different solid phases could control the fate of arsenic in this lake such as gypsum for As(V) in the hypolimnion, mackinawite for As(V) and As(III) in the hypolimnion, and close to the oxycline, Fe(III) oxyhydroxides are possible hosts for both As(III) and As(V).

The synthesis of clay minerals has been studied for decades in an attempt to better understand their formation in natural environments and more recently to obtain clay minerals with controlled compositions and properties. Even though nontronite has been synthesized successfully since 1935, the process is not a straightforward and has been poorly documented. In the present review concerning the synthesis of nontronite and other Fe-rich smectites, the experiments attempted in the past are discussed critically in light of the most recent data. Most notably, the application of relationships established recently, thanks to synthetic smectitic series, have allowed us to refine the chemical compositions of some nontronites synthesized previously.

The early Cambrian Period was a key interval in Earth history with regard to changes in both ocean chemistry and animal evolution. Although increasing ocean ventilation has been widely assumed to have played a key role in the rapid appearance, diversification and spatial colonization of early animals, this relationship is in fact not firmly established. Here, we report a high-resolution Fe-C-S-Al-Ti geochemical study of the lower Cambrian Wangjiaping section from an outer-shelf setting of the Yangtze Sea of South China. Iron speciation data document a redox transition from dominantly euxinic to ferruginous conditions during Cambrian Age 3 (c. 521–514 Ma). Interpretation of coexisting pyrite sulphur isotope (δ34Spy) records from Wangjiaping reveals relatively high marine sulphate availability at Wangjiaping. Furthermore, Wangjiaping section shows lower δ34Spy (‒2.1±5.3‰) and lower TOC (2.4±1.1%) values but higher positive correlation (R2 = 0.66, p < 0.01) between TOC and Fepy/FeHR relative to deeper sections reported previously, suggesting that euxinia developed at Wangjiaping in response to increasing marine productivity and organic matter-sinking fluxes. Our reconstructed redox conditions and fossils at Wangjiaping in comparison with previously well-studied strata in the inner-shelf Xiaotan and Shatan sections suggest that planktonic and benthic planktonic trilobites with bioturbation appeared in the oxic water columns, whereas only planktonic trilobites without bioturbation occurred within the anoxic (even euxinic) water columns during Cambrian Age 3. This finding indicates that spatial heterogeneity of redox conditions in the shelves had an important effect on early animal distribution in the Yangtze Block.