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Many nanoscale biomaterials fail to reach the clinical trial stage due to a poor understanding of the fundamental principles of their in vivo behaviour. Here we describe the transport, transformation and bioavailability of MoS 2 nanomaterials through a combination of in vivo experiments and molecular dynamics simulations. We show that after intravenous injection molybdenum is significantly enriched in liver sinusoid and splenic red pulp. This biodistribution is mediated by protein coronas that spontaneously form in the blood, principally with apolipoprotein E. The biotransformation of MoS 2 leads to incorporation of molybdenum into molybdenum enzymes, which increases their specific activities in the liver, affecting its metabolism. Our findings reveal that nanomaterials undergo a protein corona-bridged transport–transformation–bioavailability chain in vivo, and suggest that nanomaterials consisting of essential trace elements may be converted into active biological molecules that organisms can exploit. Our results also indicate that the long-term biotransformation of nanomaterials may have an impact on liver metabolism. Understanding the in vivo biotransformation of nanomaterials used for biomedical applications might shed light on their long-term effects and safety. Here the authors show that molybdenum derived from nanomaterials is mainly transported in the liver, in a corona-mediated process, and is incorporated in molybdoenzymes, with an effect on liver metabolism.

Molybdenum is toxic to ruminants when present in high levels in forage, causing physiological copper deficiency. A critical level for ruminants is 3–10 mg Mo kg−1 dry matter. The average Mo level varies considerably between different arable soils, depending mainly on soil parent material. This study investigated the possibility of using various existing sources of geospatial information (geophysical, biogeochemical and soil chemical) to develop a geography-based risk assessment system. Forage samples (n = 173) were collected in 2006–2007. Three types of national geoscientific datasets were tested: (1) SEPA topsoil, comprising data from arable land within the Swedish environmental monitoring programme; (2) SGU biogeochemical, containing data from aquatic plant root material collected in small streams; and (3) SGU geophysical, consisting of data from airborne gamma-ray scanning. The digital postcode area map was used for geocoding, with Mo concentrations in forage assigned to arable parts of the corresponding postcode area. By combining this with the three national geoscientific databases, it was possible to construct a risk map using fuzzy classification depicting High-risk, Intermediate-risk, Low-risk and Very-low-risk areas. The map was validated using 42 randomly selected samples. All samples but one with Mo > 3 mg kg−1 were found in postcode areas designated High risk. Thus, the risk map developed seems to be useful as a decision support system on where standard forage analyses need to be supplemented with Mo analyses.

Biological nitrogen fixation (BNF) by microorganisms associated with cryptogamic covers, such as cyanolichens and bryophytes, is a primary source of fixed nitrogen in pristine, high-latitude ecosystems. On land, low molybdenum (Mo) availability has been shown to limit BNF by the most common form of nitrogenase (Nase), which requires Mo in its active site. Vanadium (V) and iron-only Nases have been suggested as viable alternatives to countering Mo limitation of BNF; however, field data supporting this long-standing hypothesis have been lacking. Here, we elucidate the contribution of vanadium nitrogenase (V-Nase) to BNF by cyanolichens across a 600-km latitudinal transect in eastern boreal forests of North America. Widespread V-Nase activity was detected (∼15–50% of total BNF rates), with most of the activity found in the northern part of the transect. We observed a 3-fold increase of V-Nase contribution during the 20-wk growing season. By including the contribution of V-Nase to BNF, estimates of new N input by cyanolichens increase by up to 30%. We find that variability in V-based BNF is strongly related to Mo availability, and we identify a Mo threshold of ∼250 ng·glichen −1 for the onset of V-based BNF. Our results provide compelling ecosystem-scale evidence for the use of the V-Nase as a surrogate enzyme that contributes to BNF when Mo is limiting. Given widespread findings of terrestrial Mo limitation, including the carbon-rich circumboreal belt where global change is most rapid, additional consideration of V-based BNF is required in experimental and modeling studies of terrestrial biogeochemistry.

Data are presented that support the idea of an oxygenation event in the immediate aftermath of the Marinoan glaciation, pre-dating previous estimates for post-Marinoan oxygenation by more than 50 million years. A breath of oxygen for the early metazoans Macroscopic metazoans first appeared in the fossil record shortly after the termination of the late Cryogenian (Marinoan) glaciation about 635 million years ago. It has been suggested that an oxygenation event at about this time was the driving factor behind the rise of the metazoans, but current estimates suggest that oxygenation occurred between 580 million and 550 million years ago, well after initial animal diversification. New geochemical data from early Ediacaran organic-rich black shales of the basal Doushantuo Formation in South China now suggest that the oxidation event occurred more than 50 million years earlier, in the immediate aftermath of the Marinoan glaciation. The data provide evidence for a significant postglacial oxygenation and support a link between the most severe glaciations in Earth's history, the oxygenation of Earth's surface and the earliest emergence of complex animals. Metazoans are likely to have their roots in the Cryogenian period 1 , 2 , 3 , but there is a marked increase in the appearance of novel animal and algae fossils shortly after the termination of the late Cryogenian (Marinoan) glaciation about 635 million years ago 4 , 5 , 6 . It has been suggested that an oxygenation event in the wake of the severe Marinoan glaciation was the driving factor behind this early diversification of metazoans and the shift in ecosystem complexity 7 , 8 . But there is little evidence for an increase in oceanic or atmospheric oxygen following the Marinoan glaciation, or for a direct link between early animal evolution and redox conditions in general 9 . Models linking trends in early biological evolution to shifts in Earth system processes thus remain controversial 10 . Here we report geochemical data from early Ediacaran organic-rich black shales (∼635–630 million years old) of the basal Doushantuo Formation in South China. High enrichments of molybdenum and vanadium and low pyrite sulphur isotope values (Δ 34 S values ≥65 per mil) in these shales record expansion of the oceanic inventory of redox-sensitive metals and the growth of the marine sulphate reservoir in response to a widely oxygenated ocean. The data provide evidence for an early Ediacaran oxygenation event, which pre-dates the previous estimates for post-Marinoan oxygenation 11 , 12 , 13 by more than 50 million years. Our findings seem to support a link between the most severe glaciations in Earth’s history, the oxygenation of the Earth’s surface environments, and the earliest diversification of animals.

High-resolution chemostratigraphy reveals an episode of enrichment of the redox-sensitive transition metals molybdenum and rhenium in the late Archean Mount McRae Shale in Western Australia. Correlations with organic carbon indicate that these metals were derived from contemporaneous seawater. Rhenium/osmium geochronology demonstrates that the enrichment is a primary sedimentary feature dating to 2501 ± 8 million years ago (Ma). Molybdenum and rhenium were probably supplied to Archean oceans by oxidative weathering of crustal sulfide minerals. These findings point to the presence of small amounts of O₂ in the environment more than 50 million years before the start of the Great Oxidation Event.

The Chinese yam (Dioscorea polystachya, DP) is promising for the food and pharmaceutical industries due to its nutritional value and pharmaceutical potential. Its proper cultivation is therefore of interest. An insufficient supply of minerals necessary for plant growth can be manifested by discoloration of the leaves. In our earlier study, magnesium deficiency was excluded as a cause. As a follow-up, this work focused on manganese and molybdenum. To quantify both minerals in leaf extracts of DP, analytical methods based on atomic absorption spectrometry (AAS) using the graphite furnace sub-technique were devised. The development revealed that the quantification of manganese works best without using any of the investigated modifiers. The optimized pyrolysis and atomization temperatures were 1300 °C and 1800 °C, respectively. For the analysis of molybdenum, calcium proved to be advantageous as a modifier. The optimum temperatures were 1900 °C and 2800 °C, respectively. Both methods showed satisfactory linearity for analysis. Thus, they were applied to quantify extracts from normal and discolored leaves of DP concerning the two minerals. It was found that discolored leaves had higher manganese levels and a lower molybdenum content. With these results, a potential explanation for the discoloration could be found.

A novel method for the spectrophotometric determination of trace amounts of molybdenum has been developed. This method utilizes a centrifuge-less cloud point extraction (CL-CPE) in a mixed micellar (MM) system containing a nonionic surfactant (Triton X-114) and an ionic liquid (Aliquat® 336, A336). The chromophore chelating reagent employed was 4-nitrocatechol (4NC, H2L). This work marks its first application as a CPE reagent. Under the optimal conditions, Mo(VI) forms a yellow ternary complex with 4NC and A336, which can be represented by the formula (A336+)2[MoO2L2]. The method possesses the following characteristics: limit of detection (LOD) of 3.2 ng mL−1, linear range of 10.8–580 ng/mL, absorption maximum of 435 nm, molar absorptivity coefficient of 3.34 × 105 L mol−1 cm−1, and Sandell’s sensitivity of 0.29 ng cm−2. The method has been successfully employed for the determination of molybdenum in reference standard steel samples, bottled mineral water, and a molybdenum-containing dietary supplement.

The relationship between trace elements and neurological development is an emerging research focus. We performed a case–control study to explore (1) the differences of 13 trace elements chromium (Cr), manganese (Mn), cobalt (Co), zinc (Zn), arsenic (As), selenium (Se), molybdenum (Mo), cadmium (Cd), stannum (Sn), stibium (Sb), mercury (Hg), titanium (TI), and plumbum (Pb) concentration in whole blood and urine between autism spectrum disorder (ASD) children and their typical development peers, and (2) the association between the 13 trace elements and core behaviors of ASD. Thirty ASD subjects (cases) and 30 age-sex-matched healthy subjects from Baise City, Guangxi Zhuang Autonomous Region, China, were recruited. Element analysis was carried out by inductively coupled plasma-optical emission spectrometry. Autistic behaviors were assessed using Autism Behavior Checklist (ABC), Childhood Autism Rating Scale (CARS), and Children Neuropsychological and Behavior Scale (CNBS). The whole blood concentrations of Mo ( p  = 0.004), Cd (0.007), Sn ( p  = 0.003), and Pb ( p  = 0.037) were significantly higher in the ASD cases than in the controls. Moreover, Se (0.393), Hg (0.408), and Mn (− 0.373) concentrations were significantly correlated between whole blood and urine levels in ASD case subjects. There were significant correlations between whole blood Sb (0.406), Tl (0.365), Mo (− 0.4237), Mn (− 0.389), Zn (0.476), and Se (0.375) levels and core behaviors of ASD. Although the mechanism of trace element imbalance in ASD is unclear, these data demonstrate that core behaviors of ASD may be affected by certain trace elements. Further studies are recommended for exploring the mechanism of element imbalance and providing corresponding clinical treatment measures.

The contamination of soils by heavy metals from the mining industry nowadays is one of the greatest threats to environment and human health. The cleaning of polluted soils using cost-effective and eco-friendly methods such as phytoextraction has wide public recognition. Considering the above-mentioned ones, the objectives of the present study were the identification of Cu and Mo accumulation capability and the phytoextraction potential of Melilotus officinalis and Amaranthus retroflexus as well as the determination of the influence of ammonium nitrate and EDTA on phytoextraction effectiveness. The contaminated soil samples for phytoremediation experiments under ex situ conditions were collected from the surroundings of the Zangezur Copper and Molybdenum Combine, Armenia. During the studies, it was found out that M. officinalis and A. retroflexus are capable of growing in polluted soils. M. officinalis grown in polluted soil had greater ability to accumulate heavy metals in roots, while the ability to transport the copper to aboveground parts was more pronounced in A. retroflexus. During the growing of these plant species for phytoextraction of soils contaminated by copper, it is necessary to use chelates, in particular the EDTA, for the enhancement of the effectiveness of phytoextraction process. EDTA due to chelating influence increased the availability of copper for plants and its mobility in them that lead to greater accumulation of this metal in shoots. The application of chelates did not have a significant impact on molybdenum accumulation intensity in plants; therefore, in case of this metal, it is unreasonable to use additional chelating compounds.

Oxygen steps in the ocean The oxygenation of the Earth's atmosphere is thought to have occurred in two steps near the beginning and the end of the Proterozoic eon, around 2,500 to 550 million years ago. The oxidation state of the ocean between these two steps and the timing of deep ocean oxygenation, however, remain poorly known. Scott et al . now use molybdenum and total organic carbon data from black shales to track the redox state of the ocean at this time. Molybdenum is an essential participant in nutrient cycling, and its availability is highly sensitive to Earth's redox state. The results provide a new narrative for the historical texture of Earth's oxygenation, and will be of relevance for the study of the events that presaged the appearance of animals on Earth. Molybdenum and total organic carbon data from black shales is used to gain insights into the redox state of the ocean. The data suggests mild oxidative weathering of the continents before ∼2,200 Myr ago, but weathering becomes more persistent and vigorous at ∼2,150 Myr ago, 200 million years after the initial rise in atmospheric oxygen. Limited availability of molybdenum after 1,800 Myr ago may have acted as a negative nutrient feedback limiting the spatial and temporal extent of sulphidic conditions. Biogeochemical signatures preserved in ancient sedimentary rocks provide clues to the nature and timing of the oxygenation of the Earth’s atmosphere. Geochemical data 1 , 2 , 3 , 4 , 5 , 6 suggest that oxygenation proceeded in two broad steps near the beginning and end of the Proterozoic eon (2,500 to 542 million years ago). The oxidation state of the Proterozoic ocean between these two steps and the timing of deep-ocean oxygenation have important implications for the evolutionary course of life on Earth but remain poorly known. Here we present a new perspective on ocean oxygenation based on the authigenic accumulation of the redox-sensitive transition element molybdenum in sulphidic black shales. Accumulation of authigenic molybdenum from sea water is already seen in shales by 2,650 Myr ago; however, the small magnitudes of these enrichments reflect weak or transient 7 sources of dissolved molybdenum before about 2,200 Myr ago, consistent with minimal oxidative weathering of the continents. Enrichments indicative of persistent and vigorous oxidative weathering appear in shales deposited at roughly 2,150 Myr ago, more than 200 million years after the initial rise in atmospheric oxygen 1 , 2 . Subsequent expansion of sulphidic conditions after about 1,800 Myr ago (refs 8 , 9 ) maintained a mid-Proterozoic molybdenum reservoir below 20 per cent of the modern inventory, which in turn may have acted as a nutrient feedback limiting the spatiotemporal distribution of euxinic (sulphidic) bottom waters and perhaps the evolutionary and ecological expansion of eukaryotic organisms 10 . By 551 Myr ago, molybdenum contents reflect a greatly expanded oceanic reservoir due to oxygenation of the deep ocean and corresponding decrease in sulphidic conditions in the sediments and water column.