Using X-ray computed tomography and micro-Raman spectrometry to measure individual particle surface area, volume, and morphology towards investigating atmospheric heterogeneous reactions

Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogeneous reactions usually have large variations and may not be relevant to real atmospheric conditions. One of the major reasons for this is the use of bulk samples in laboratory experiments, while particles in the atmosphere are suspended individually. A number of technologies have been developed recently to study heterogeneous reactions on the surfaces of individual particles. Precise measurements on the reactive surface area, volume, and morphology of individual particles are necessary for calculating the uptake coefficient, quantifying reactants and products, and understanding the reaction mechanism better. In this study, for the first time we used synchrotron radiation X-ray computed tomography(XCT) and micro-Raman spectrometry to measure individual CaCO_3 particle morphology, with sizes ranging from 3.5–6.5 μm. Particle surface area and volume were calculated using a reconstruction method based on software threedimensional(3-D) rendering. The XCT was first validated with high-resolution fieldemission scanning electron microscopy(FE-SEM) to acquire accurate CaCO_3 particle surface area and volume estimates. Our results showed an average difference of only 6.1% in surface area and 3.2% in volume measured either by micro-Raman spectrometry or X-ray tomography. X-ray tomography and FE-SEM can provide more morphological details of individual Ca CO3 particles than micro-Raman spectrometry. This study demonstrated that X-ray computed tomography and micro-Raman spectrometry can precisely measure the surface area, volume, and morphology of an individual particle.     

受限空间瓦斯爆炸链式反应机理的敏感性分析

瓦斯爆炸是一种复杂的链式反应,为了探求其链式反应的动力学特性,采用详细的瓦斯爆炸链式反应机理(包括53种组分,325个反应),利用软件CHEMKINⅢ中的SENKIN子程序包,利用SENKIN子程序包中的敏感性分析程序块对瓦斯爆炸的详细化学反应机理进行分析,找出对瓦斯爆炸过程反应动力学特性影响较大的反应步。通过数值计算和模拟,对瓦斯爆炸过程中反应物浓度、自由基以及致灾性气体的生成和变化做了敏感性分析,得出了影响瓦斯爆炸的关键反应步为R158,R53,R98,R57,R155,R156,R38,R32,R119。     

Dimer formation during UV photolysis of diclofenac

Dimer formation was observed during ultraviolet (UV) photolysis of the anti-inflammatory drug diclofenac, and confirmed with mass spectrometry, NMR and fluorescence analysis. The dimers were combinations of the two parent molecules or of the parent and the product of photolysis, and had visible color. Radical formation during UV exposure and dissolved oxygen photosensitized reactions played a role in dimer formation. Singlet oxygen formed via photosensitization by photolysis products of diclofenac. It reacted with diclofenac to form an epoxide which is an intermediate in some dimer formation pathways. Quantum yield of photolysis for diclofenac was 0.21 ± 0.02 and 0.19 ± 0.02 for UV irradiation from medium pressure and low pressure mercury vapor lamps, respectively. Band pass filter experiments revealed that the quantum yield is constant at wavelengths >200 nm. The same dimers formed in laboratory grade water when either of the two UV sources was used. Dimers did not form in wastewater effluent matrix, and diclofenac epoxide molecules may have formed bonds with organic matter rather than each other Implications for the importance of dimer formation in NOM are discussed.     

Abiotic transformation of estrogens in synthetic municipal wastewater: An alternative for treatment?

The abiotic transformation of estrogens, including estrone (E1), estradiol (E2), estriol (E3) and ethinylestradiol (EE2), in the presence of model vegetable matter was confirmed in this study. Batch experiments were performed to model the catalytic conversion of E1, E2, E3 and EE2 in synthetic wastewater. Greater than 80% reduction in the parent compounds was achieved for each target chemical after 72 h with the remaining concentration distributed between aqueous and solid phases as follows: 13% and 7% for E1, 10% and 2% for E2, 6% and 2% for E3, and 8% and 3% for EE2, respectively. Testosterone, androstenedione and progesterone were also monitored in this study, and their concentrations were found to be in agreement with initially spiked amount. Data collected under laboratory conditions provided the basis for implementing new abiotic wastewater treatment technologies that use inexpensive materials.     

钙基烟气脱硫剂制备的实验研究

采用正交实验 ,研究了水合制备高效钙基烟气脱硫剂时各制备条件对产物的影响。结果表明 ,水合时间、水合温度Ca(OH) 2 /CaSO4的质量比 ,以及飞灰 / (Ca(OH) 2 +CaSO4)质量比四个条件对脱硫剂比表面积的形成有显著的影响 ;从而由单因素实验得出一最佳钙基脱硫剂制备条件组合。此外 ,通过XDR分析 ,测定了脱硫剂的物相组成 ,扫描电镜观察显示飞灰和水合吸收剂具有不同的表面形态     

Aqueous free radical chemistry of mercury in the presence of iron oxides and ambient aerosol

The effect of goethite (α-FeOOH), hematite (α-Fe₂0₃) and maghemite (γ-Fe₂0₃) on the aqueous photoreduction of divalent mercury with organic acids (oxalate, formate and acetate) is investigated. Laboratory photochemistry experiments with synthetic iron oxides and simulated sunlight were performed to assess the role of the oxides on the photoreduction. Ambient aerosol was also collected and introduced as the solid phase to compare its effect with that of synthetic oxides. It is observed that the presence of various iron oxides or aerosol particles enhances the photoreduction. It is also found that the hydroxyl radicals produced in the hematite-oxalate systems can re-oxidize the reduced mercury back to Hg(II). Based on the experimental observations, mechanisms responsible for the Hg(II) reduction are proposed. The kinetics of Hg⁰ oxidation by hydroxyl radicals was also studied by a steady-state kinetic technique using nitrate photolysis as the * OH radical source. The second-order rate constant is determined to be 2.0 × 10⁹ M⁻ s⁻¹. The implications of the studied reactions on the atmospheric chemistry of mercury are discussed.     

类芬顿反应对长期施肥土壤中有机碳的影响

以吉林公主岭、江西进贤、湖南祁阳、辽宁沈阳农大等多地长期定位试验站的土壤为研究对象,结合原位微宇宙试验培养的土壤,探索类芬顿反应对长期施肥土壤中有机碳的影响.结果表明,长期施用化肥的土壤中自由基含量均显著低于长期施用有机肥的土壤.通过纳米粒子探针(NanoSIMS)发现,施用化肥的土壤中56Fe16O-的离子强度强于施...     

Revealing the GHG reduction potential of emerging biomass-based CO2 utilization with an iron cycle system

● Greenhouse gas mitigation by biomass-based CO₂ utilization with a Fe cycle system. ● The system including hydrothermal CO₂ reduction with Fe and Fe recovery by biomass. ● The reduction potential quantified by experiments, simulations, and an ex-ante LCA. ● The greatest GHG reduction potential is −34.03 kg CO₂-eq/kg absorbed CO₂. ● Ex-ante LCA supports process optimization to maximize GHG reduction potential. CO₂ utilization becomes a promising solution for reducing anthropogenic greenhouse gas (GHG) emissions. Biomass-based CO₂ utilization (BCU) even has the potential to generate negative emissions, but the corresponding quantitative evaluation is limited. Herein, the biomass-based CO₂ utilization with an iron cycle (BCU-Fe) system, which converts CO₂ into formate by Fe under hydrothermal conditions and recovers Fe with biomass-derived glycerin, was investigated. The GHG reduction potential under various process designs was quantified by a multidisciplinary method, including experiments, simulations, and an ex-ante life-cycle assessment. The results reveal that the BCU-Fe system could bring considerable GHG emission reduction. Significantly, the lowest value is −34.03 kg CO₂-eq/kg absorbed CO₂ (−2.44 kg CO₂-eq/kg circulated Fe) with the optimal yield of formate (66%) and Fe (80%). The proposed ex-ante evaluation approach not only reveals the benefits of mitigating climate change by applying the BCU-Fe system, but also serves as a generic tool to guide the industrialization of emerging carbon-neutral technologies.     

Workplace racial/ethnic similarity,job satisfaction,and lumbar back health among warehouse workers: Asymmetric reactions across racial/ethnic groups

Racial and ethnic minority employees constitute a significant proportion of the U.S. workforce. The literature on demographic similarity in the workplace suggests that the proportion of co‐workers who share the same racial/ethnic background (racial/ethnic similarity) can influence job attitudes and employee well‐being and that the reactions to racial/ethnic similarity may differ between the racially dominant and subordinate groups. This study applies status construction theory to examine the extent to which racial/ethnic similarity is associated with job satisfaction and lumbar back health among warehouse employees. We surveyed 361 warehouse workers (204 whites, 94 African‐Americans, and 63 Latino workers) in 68 jobs in nine distribution centers in the United States. Multilevel analyses indicate that white and racial/ethnic minority groups react differently to racial/ethnic similarity. For job satisfaction, white employees experience higher job satisfaction when they are highly racially/ethnically similar to their colleagues, whereas Latino employees experience higher job satisfaction when they are racially/ethnically dissimilar to others. As for lumbar back health, among Latino and African‐American employees, higher racial/ethnic similarity is associated with better lumbar back health whereas for white employees, the association is the opposite. Across all groups, moderate levels of racial/ethnic similarity were associated with the best lumbar back health. Copyright © 2013 John Wiley & Sons, Ltd.