Testing Iron Stable Isotope Ratios as a Signature of Biomass Burning

Biomass burning is an important source of soluble Fe transported to the open ocean; however, its exact contribution remains unclear. Iron isotope ratios can be used as a tracer because Fe emitted by combustion can yield very low Fe isotope ratios due to isotope fractionation during evaporation processes. However, data on Fe isotope ratios of aerosol particles emitted during biomass burning are lacking. We collected size-fractionated aerosol samples before, during, and after a biomass burning event and compared their Fe isotope ratios. On the basis of the concentrations of several elements and Fe species, Fe emitted during the event mainly comprised suspended soil particles in all the size fractions. Iron isotope ratios of fine particles before and after the event were low due to the influence of other anthropogenic combustion sources, but they were closer to the crustal value during the event because of the influence of Fe from suspended soil. Although Fe isotope ratios of soluble Fe were also measured to reduce Fe from soil components, we did not find low isotope signals. Results suggested that Fe isotope ratios could not identify Fe emitted by biomass burning, and low Fe isotope ratios are found only when the combustion temperature is high enough for a sufficient amount of Fe to evaporate

High-Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy for the Speciation of Fe in Aerosol Samples

In this study, we compared the high-energy resolution X-ray fluorescence X-ray absorption near-edge structure (HERFD-XANES) and normal XANES spectra of various iron (Fe) species and Fe in atmospheric aerosol samples to explore the advantages of Fe K-edge HERFD-XANES for Fe speciation in aerosols using the linear combination fitting (LCF) of XANES spectra. We also conducted Fe extraction experiments to validate the LCF-XANES. In the HERFD-XANES spectra, the pre-edge region showed specific structures absent in normal XANES. HERFD-XANES also produced more distinctive shoulders within each spectrum than normal XANES. HERFD-XANES was applied to an aerosol sample (MT21-S2) collected in Tokyo, Japan. Normal XANES identified ferrihydrite, biotite, and montmorillonite, whereas HERFD-XANES clearly detected goethite as a fourth component. Normal XANES did not distinguish between ferrihydrite and goethite in LCF because of their similar structures. A similar trend was observed in the pre-edge region, and the Fe extraction experiment result was consistent with the LCF result in the pre-edge region. Thus, LCF of HERFD-XANES, in particular for the pre-edge region, can be a powerful tool for Fe speciation in aerosols

Comparison of Arsenate and Molybdate Speciation in Hydrogenetic Ferromanganese Nodules

Marine ferromanganese oxides contain a large amount of trace elements, such as arsenic (As) and molybdenum (Mo). However, the host phases of tetrahedral AsO43- and MoO42- oxyanions therein have not been clearly identified thus far. In this work, we explored the mineralogical components of hydrogenetic (HG) ferromanganese nodules and compared the distribution behaviors of As and Mo. The X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) analyses showed that the predominant manganese and iron phases were vernadite (delta-MnO2) and ferrihydrite, respectively. According to the sequential extraction examination, both As and Mo were associated with the iron (oxyhydr)oxide phases. However, the XAS analyses indicated that As was retained by the ferrihydrite phase via double corner-shared complexation, while Mo was preferentially adsorbed on delta-MnO2 via edge-shared complexation. The immobilization of As and Mo by HG ferromanganese samples was attributed to specific chemical binding (Delta G(chem)) rather than Coulombic interaction (Delta G(coul)) as proposed in previous studies. The comparison of Mo XAS spectra before and after extraction revealed the unreliability of the sequential extraction approach to determine the host phase of trace elements as a result of the potential readsorption risk. The different distribution trends of As and Mo were due to their disparate intrinsic properties (e.g., averaged dissociation constants of conjugate acids) and the diverse properties (i.e., surface site densify, adsorption equilibrium constant, and crystalline structure) of ferrihydrite and delta-MnO2. These research findings would be significant for evaluating the geochemical behaviors and environmental fate of trace elements in marine systems

Radiation makes cells select the form of death dependent on external or internal exposure: apoptosis or pyroptosis

Abstract Internal radiation exposure from neutron-induced radioisotopes environmentally activated following atomic bombing or nuclear accidents should be considered for a complete picture of pathologic effects on survivors. Acute and localized high dose radiation exposure from hot particles taken into the body must induce cell death and severe damage to tissues, whether they are proliferating or not. However, very little the cellular and molecular mechanisms underlying this internal radiation pathology has been investigated. Male Wistar rats were internally exposed to 56MnO2 powder by inhalation. Small intestine samples were investigated by histological staining at acute phase (6 h, 3 days and 14 days) and late phase (2, 6 and 8 months) after the exposure. Histological location and chemical properties of the hot particles embedded in small intestinal tissues were analyzed by synchrotron radiation—X-ray fluorescence—X-ray absorption near-edge structure (SR–XRF–XANES). Hot particles located in the intestinal cavity were identified as accumulations of Mn and iron. Pathological changes showed evidence of crypt shortening, massive cell death at the position of stem cell zone, including apoptosis and pyroptosis from 6 h through 8 months in the internal exposed rats

Impact of Local High Doses of Radiation by Neutron Activated Mn Dioxide Powder in Rat Lungs: Protracted Pathologic Damage Initiated by Internal Exposure

Internal radiation exposure from neutron-induced radioisotopes environmentally activated following atomic bombing or nuclear accidents should be considered for a complete picture of pathologic effects on survivors. Inhaled hot particles expose neighboring tissues to locally ultra-high doses of β-rays and can cause pathologic damage. 55MnO2 powder was activated by a nuclear reactor to make 56MnO2 which emits β-rays. Internal exposures were compared with external-rays. Male Wistar rats were administered activated powder by inhalation. Lung samples were observed by histological staining at six hours, three days, 14 days, two months, six months and eight months after the exposure. Synchrotron radiation-X-ray fluorescence-X-ray absorption near-edge structure (SR-XRF-XANES) was utilized for the chemical analysis of the activated 56Mn embedded in lung tissues. 56Mn beta energy spectrum around the particles was calculated to assess the local dose rate and accumulated dose. Hot particles located in the bronchiole and in damaged alveolar tissue were identified as accumulations of Mn and iron. Histological changes showed evidence of emphysema, hemorrhage and severe inflammation from six hours through eight months. Apoptosis was observed in the bronchiole epithelium. Our study shows early event damage from the locally ultra-high internal dose leads to pathogenesis. The trigger of emphysema and hemorrhage was likely early event damage to blood vessels integral to alveolar walls