Experimental studies on the formation of pyrite and marcasite and the mechanisms of arsenic incorporation

Iron disulfide (FeS2) has two polymorphs, pyrite and marcasite. Pyrite is the most abundant sulfide in the Earth's crust. Both minerals can host economic amount of gold and environmentally hazardous arsenic and are found to coexist in hydrothermal mineralization. With time, thermodynamically metastable marcasite can transform to pyrite. However, the kinetics of the marcasite to pyrite transformation, and the mechanisms of arsenic incorporation during growth of pyrite are not well-constrained. This thesis presents experimental results and discussions on: (i) the formation of pyrite and marcasite under dry and hydrothermal conditions (Chapter 2 and 3), and (ii) incorporation of arsenic into pyrite during the growth of pyrite on pyrite seeds (Chapter 4). In Chapter 2, the transformation from marcasite to pyrite was studied by in situ synchrotron powder X-ray diffraction (PXRD) at 520 °C and 540 °C, and ex situ anneal/quench experiments at 400 °C, 462 °C, and 520 °C. It was found that the mechanism and kinetics of this transformation depend not only on temperature, but also on particle size, the presence of water vapor, and the presence of pyrite inclusions in marcasite. Under dry conditions, the transformation is limited by surface nucleation and occurs via epitaxial nucleation of pyrite on marcasite, with {100}pyrite//{101}marcasite and {001}pyrite//{010}marcasite. In contrast, in the presence of water vapor, there is little crystallographic orientation relationship between the two phases; the transformation is limited by surface nucleation, but modification of the surface properties by water vapor results in a different nucleation mechanism, and consequently different kinetics. Kinetic analysis estimates a half-life of 1.5 Ma at 300 °C for the transformation under dry conditions with pyrite-free marcasite grains (<38 μm), but this estimation should be used with extreme caution due to the complexity of the process. From synchrotron X-ray fluorescence elemental mapping, trace elements (As and Pb) play an insignificant role in the transformation. However, the presence of a fluid phase changes the behavior of Pb. Under dry conditions randomly oriented particles of galena formed in pyrite, while under water vapor conditions arrays of nano-to-microparticles of galena precipitated in pores. This chapter highlights that although the natural occurrence of marcasite can indicate low temperature environments, precise estimation of temperature should not be made without considering the influences from various reaction parameters. In Chapter 3, combined in-situ synchrotron PXRD and ex situ experiments were conducted under hydrothermal conditions at 190 °C and 210 °C and pH 1, aiming to study the controls on the precipitation of pyrite and marcasite from supersaturated hydrothermal solutions and the kinetics of hydrothermal transformation from marcasite to pyrite. In situ PXRD experiments show the important role of saturation index on the precipitation of pyrite and marcasite; at 190 °C, hydrothermal fluids rich in ΣS(-II) (0.9 mM) favors the precipitation of nanocrystalline pyrite (23 nm) due to high saturation index, while S(-II)-free fluids produce a mixture of marcasite and pyrite nanocrystals (21-46 nm) due to low saturation index. Fluid/rock ratio (70 and 120 g/g at 210 °C) can affect saturation index of the fluids, resulting in complex nucleation and crystal growth dynamics such as the evolution of crystallite size, phase abundance, and pyrite/marcasite ratio. Ex situ experiments show the rapid transformation from marcasite to pyrite at 210 °C; around 83% marcasite is transformed to pyrite in just 3 weeks, compared to 4.3 million years or 6.3 trillion years at 210 °C based on extrapolation using the kinetic models reported in early studies under dry conditions. These results suggest that saturation index influences the dynamics of precipitation under hydrothermal conditions and controls the phase selection between pyrite and marcasite, and that marcasite may not survive over geological time in low temperature environments in the presence of acidic hydrothermal fluids. In Chapter 4, the formation of zoned arsenian pyrite was studied by growing pyrite on pyrite seeds in O2-free, As-enriched fluids at 200 °C and pH 7. The distribution and concentrations of As in pyrite, as well as the morphology of the zoning are influenced by sulfur source; i.e., native sulfur or Na2S2O3·5H2O. For experiments with native sulfur, up to four concentric alternate zones of As-rich (first zone on pyrite seed) and As-free pyrite grow on pyrite seeds. For experiments with Na2S2O3·5H2O, an aggregate of concentrically zoned pyrite microparticles (~1 µm) precipitate on the surface of pyrite seeds. Based on EMPA, the maximum concentration of As is 4.3 wt. %. However, the TEM-EDS analyses reveal ≤5.8 wt. % of As. HRTEM and selected area electron diffraction (SAED) pattern combined with EBSD analyses document epitaxial growth of As-pyrite on pyrite seed in the presence of native sulfur, but aggregation of randomly oriented aggregates of pyrite microparticles in the presence of thiosulfate. High-angle annular dark-field scanning TEM (HAADF-STEM), HRTEM observations, and EDS mapping show a sharp boundary and trails of pores between the pyrite seed and the product and between the growth zones. In the presence of native sulfur, the thickness of the As-pyrite growth zones is ~ 50 nm, while the subsequently formed growth zones of “barren” pyrite are ~5000 nm thick. X-ray absorption near edge structure (XANES) analyses reveal that speciation of As in pyrite depends on the S-source: (i) anionic As(-I) substitutes for S in pyrite as As2 pair when native S is used, and (ii) cationic As(II)/As(III) substitutes for Fe when thiosulfate is used. Our experiments show that the incorporation of As into pyrite and the formation and morphology of pyrite growth zones are controlled by the source of sulfur in hydrothermal fluids. This thesis highlights the factors that control the mechanisms of the formation and transformation of pyrite and marcasite and the dependence of As incorporation into arsenian pyrite structure as a function of S and As source in the presence of pyrite seeds. These outcomes should benefit our understanding of the formation and alteration of Carlin-type, epithermal, volcanic-hosted massive sulfide (VMS), and orogenic Au deposits

Ndrg2 regulates vertebral specification in differentiating somites

AbstractIt is generally thought that vertebral patterning and identity are globally determined prior to somite formation. Relatively little is known about the regulators of vertebral specification after somite segmentation. Here, we demonstrated that Ndrg2, a tumor suppressor gene, was dynamically expressed in the presomitic mesoderm (PSM) and at early stage of differentiating somites. Loss of Ndrg2 in mice resulted in vertebral homeotic transformations in thoracic/lumbar and lumbar/sacral transitional regions in a dose-dependent manner. Interestingly, the inactivation of Ndrg2 in osteoblasts or chondrocytes caused defects resembling those observed in Ndrg2−/− mice, with a lower penetrance. In addition, forced overexpression of Ndrg2 in osteoblasts or chondrocytes also conferred vertebral defects, which were distinct from those in Ndrg2−/− mice. These genetic analyses revealed that Ndrg2 modulates vertebral identity in segmented somites rather than in the PSM. At the molecular level, combinatory alterations of the amount of Hoxc8-11 gene transcripts were detected in the differentiating somites of Ndrg2−/− embryos, which may partially account for the vertebral defects in Ndrg2 mutants. Nevertheless, Bmp/Smad signaling activity was elevated in the differentiating somites of Ndrg2−/− embryos. Collectively, our findings unveiled Ndrg2 as a novel regulator of vertebral specification in differentiating somites

Bilirubin Restrains the Anticancer Effect of Vemurafenib on BRAF-Mutant Melanoma Cells Through ERK-MNK1 Signaling

Melanoma, the most threatening cancer in the skin, has been considered to be driven by the carcinogenic RAF-MEK1/2-ERK1/2 signaling pathway. This signaling pathway is usually mainly dysregulated by mutations in BRAF or RAS in skin melanomas. Although inhibitors targeting mutant BRAF, such as vemurafenib, have improved the clinical outcome of melanoma patients with BRAF mutations, the efficiency of vemurafenib is limited in many patients. Here, we show that blood bilirubin in patients with BRAF-mutant melanoma treated with vemurafenib is negatively correlated with clinical outcomes. In vitro and animal experiments show that bilirubin can abrogate vemurafenib-induced growth suppression of BRAF-mutant melanoma cells. Moreover, bilirubin can remarkably rescue vemurafenib-induced apoptosis. Mechanically, the activation of ERK-MNK1 axis is required for bilirubin-induced reversal effects post vemurafenib treatment. Our findings not only demonstrate that bilirubin is an unfavorable for patients with BRAF-mutant melanoma who received vemurafenib treatment, but also uncover the underlying mechanism by which bilirubin restrains the anticancer effect of vemurafenib on BRAF-mutant melanoma cells

Spatial Variabilities of Runoff Erosion and Different Underlying Surfaces in the Xihe River Basin

Runoff erosion capacity has significant effects on the spatial distribution of soil erosion and soil losses. But few studies have been conducted to evaluate these effects in the Loess Plateau. In this study, an adjusted SWAT model was used to simulate the hydrological process of the Xihe River basin from 1993 to 2012. The spatial variabilities between runoff erosion capacity and underlying surface factors were analyzed by combining spatial gradient analysis and GWR (Geographically Weighted Regression) analysis. The results show that the spatial distribution of runoff erosion capacity in the studying area has the following characteristics: strong in the north, weak in the south, strong in the west, and weak in the east. Topographic factors are the dominant factors of runoff erosion in the upper reaches of the basin. Runoff erosion capacity becomes stronger with the increase of altitude and gradient. In the middle reaches area, the land with low vegetation coverage, as well as arable land, show strong runoff erosion ability. In the downstream areas, the runoff erosion capacity is weak because of better underlying surface conditions. Compared with topographic and vegetation factors, soil factors have less impact on runoff erosion. The red clay and mountain soil in this region have stronger runoff erosion capacities compared with other types of soils, with average runoff modulus of 1.79 &#215; 10&#8722;3 m3/s&#183;km2 and 1.68 &#215; 10&#8722;3 m3/s&#183;km2, respectively, and runoff erosion power of 0.48 &#215; 10&#8722;4 m4/s&#183;km2 and 0.34 &#215; 10&#8722;4 m4/s&#183;km2, respectively. The runoff erosion capacity of the alluvial soil is weak, with an average runoff modulus of 0.96 &#215; 10&#8722;3 m3/s&#183;km2 and average erosion power of 0.198 &#215; 10&#8722;4 m4/s&#183;km2. This study illustrates the spatial distribution characteristics and influencing factors of hydraulic erosion in the Xihe River Basin from the perspective of energy. It contributes to the purposeful utilization of water and soil resources in the Xihe River Basin and provides a theoretical support for controlling the soil erosion in the Hilly-gully region of the Loess Plateau

A Flow-Through Reaction Cell for Studying Minerals Leaching by In-Situ Synchrotron Powder X-ray Diffraction

A flow-through reaction cell has been developed for studying minerals leaching by in-situ time-resolved powder X-ray diffraction, allowing for a better understanding of the leaching mechanisms and kinetics. The cell has the capability of independent control of temperature (up to 95 &deg;C) and flow rate (&gt;0.5 mL min&minus;1) for atmospheric pressure leaching. It was successfully tested at the powder diffraction beamline at the Australian Synchrotron. Galena powder was leached in a citrate solution under flow-through condition at a flow rate of 0.5 mL min&minus;1, while diffraction patterns were collected during the entire leaching process, showing rapid galena dissolution without the formation of secondary mineral phases. The flow-through cell can be used to study leaching processes of other ore minerals

Measuring Impacts of Urban Environmental Elements on Housing Prices Based on Multisource Data—A Case Study of Shanghai, China

Diverse urban environmental elements provide health and amenity value for residents. People are willing to pay a premium for a better environment. Thus, it is essential to assess the benefits and values of these environmental elements. However, limited by the interpretability of the machine learning model, existing studies cannot fully excavate the complex nonlinear relationships between housing prices and environmental elements, as well as the spatial variations of impacts of urban environmental elements on housing prices. This study explored the impacts of urban environmental elements on residential housing prices based on multisource data in Shanghai. A SHapley Additive exPlanations (SHAP) method was introduced to explain the impacts of urban environmental elements on housing prices. By combining the ensemble learning model and SHAP, the contributions of environmental characteristics derived from street view data and remote sensing data were computed and mapped. The experimental results show that all the urban environmental characteristics account for 16 percent of housing prices in Shanghai. The relationships between housing prices and two green characteristics (green view index from street view data and urban green coverage rate from remote sensing) are both nonlinear. Shanghai&rsquo;s homebuyers are willing to pay a premium for green only when the green view index or urban green coverage rate are of higher value. However, there are significant differences between the impacts of the green view index and urban green coverage rate on housing prices. The sky view index has a negative influence on housing prices, which is probably because the high-density and high-rise residential area often has better living facilities. Residents in Shanghai are willing to pay a premium for high urban water coverage. The case of Shanghai shows that the proposed framework is practical and efficient. This framework is believed to provide a tool to inform the decisions of housing buyers, property developers and policies concerning land-selling and buying, property development and urban environment improvement

NPP-VIIRS DNB Daily Data in Natural Disaster Assessment: Evidence from Selected Case Studies

Whereas monthly and annual nighttime light (NTL) composite datasets are being increasingly used to estimate socioeconomic status, use of the National Polar-orbiting Partnership Visible Infrared Imaging Radiometer Suite (NPP-VIIRS) Day/Night Band (DNB) daily data has been limited for detecting and assessing the impact of short-term disastrous events. This study explores the application of daily NPP-VIIRS DNB data in assessing the impact of three types of natural disasters: earthquakes, floods, and storms. Daily DNB images one month prior to and 10 days after a disastrous event were collected and a Percent of Normal Light (PNL) image was produced as the ratio of the mean DNB radiance of the pre- and post-disaster images. Areas with a PNL value lower than one were considered as being affected by the event. The results were compared with the damaged proxy map and the flood proxy map generated using synthetic aperture radar data as well as the reported power outage rates. Our analyses show that overall NPP-VIIRS DNB daily data are useful for detecting damages and power outages caused by earthquake, storm, and flood events. Cloud coverage was identified as a major limitation in using the DNB daily data; rescue activities, traffic, and socioeconomic status of the areas also affect the use of DNB daily data in assessing the impact of natural disasters. Our findings offer new insight into the use of the daily DNB data and provide a practical guide for researchers and practitioners who may consider using such data in different situations or regions

Investigating the Potential of Using POI and Nighttime Light Data to Map Urban Road Safety at the Micro-Level: A Case in Shanghai, China

The way in which the occurrence of urban traffic collisions can be conveniently and precisely predicted plays an important role in traffic safety management, which can help ensure urban sustainability. Point of interest (POI) and nighttime light (NTL) data have always been used for characterizing human activities and built environments. By using a district of Shanghai as the study area, this research employed the two types of urban sensing data to map vehicle&ndash;pedestrian and vehicle&ndash;vehicle collision risks at the micro-level by road type with random forest regression (RFR) models. First, the Network Kernel Density Estimation (NKDE) algorithm was used to generate the traffic collision density surface. Next, by establishing a set of RFR models, the observed density surface was modeled with POI and NTL variables, based on different road types and periods of the day. Finally, the accuracy of the models and the predicted outcomes were analyzed. The results show that the two datasets have great potential for mapping vehicle&ndash;pedestrian and vehicle&ndash;vehicle collision risks, but they should be carefully utilized for different types of roads and collision types. First, POI and NTL data are not applicable to the modeling of traffic collisions that happen on expressways. Second, the two types of sensing data are quite suitable for estimating the occurrence of traffic collisions on arterial and secondary trunk roads. Third, while the two datasets are capable of predicting vehicle&ndash;pedestrian collision risks on branch roads, their ability to predict vehicle safety on branch roads is limited

Foxp1 Regulates the Proliferation of Hair Follicle Stem Cells in Response to Oxidative Stress during Hair Cycling.

Hair follicle stem cells (HFSCs) in the bugle circularly generate outer root sheath (ORS) through linear proliferation within limited cycles during anagen phases. However, the mechanisms controlling the pace of HFSC proliferation remain unclear. Here we revealed that Foxp1, a transcriptional factor, was dynamically relocated from the nucleus to the cytoplasm of HFSCs in phase transitions from anagen to catagen, coupled with the rise of oxidative stress. Mass spectrum analyses revealed that the S468 phosphorylation of Foxp1 protein was responsive to oxidative stress and affected its nucleocytoplasmic translocation. Foxp1 deficiency in hair follicles led to compromised ROS accrual and increased HFSC proliferation. And more, NAC treatment profoundly elongated the anagen duration and HFSC proliferation in Foxp1-deficient background. Molecularly, Foxp1 augmented ROS levels through suppression of Trx1-mediated reductive function, thereafter imposing the cell cycle arrest by modulating the activity of p19/p53 pathway. Our findings identify a novel role for Foxp1 in controlling HFSC proliferation with cellular dynamic location in response to oxidative stress during hair cycling

Ectodermal Wnt signaling regulates abdominal myogenesis during ventral body wall development

AbstractDefects of the ventral body wall are prevalent birth anomalies marked by deficiencies in body wall closure, hypoplasia of the abdominal musculature and multiple malformations across a gamut of organs. However, the mechanisms underlying ventral body wall defects remain elusive. Here, we investigated the role of Wnt signaling in ventral body wall development by inactivating Wls or β-catenin in murine abdominal ectoderm. The loss of Wls in the ventral epithelium, which blocks the secretion of Wnt proteins, resulted in dysgenesis of ventral musculature and genito-urinary tract during embryonic development. Molecular analyses revealed that the dermis and myogenic differentiation in the underlying mesenchymal progenitor cells was perturbed by the loss of ectodermal Wls. The activity of the Wnt-Pitx2 axis was impaired in the ventral mesenchyme of the mutant body wall, which partially accounted for the defects in ventral musculature formation. In contrast, epithelial depletion of β-catenin or Wnt5a did not resemble the body wall defects in the ectodermal Wls mutant. These findings indicate that ectodermal Wnt signaling instructs the underlying mesodermal specification and abdominal musculature formation during ventral body wall development, adding evidence to the theory that ectoderm-mesenchyme signaling is a potential unifying mechanism for the origin of ventral body wall defects