An economic and sensitive method for extracting chromium speciation in airborne inhalable dust,using a green sample treatment coupled with electrothermal atomic absorption

ABSTRACT

A new approach of cloud point extraction CPE procedure is optimized for hexavalent chromium determination in airborne dusts. Triton X-114 is used as a surfactant and 1-(2-pyridylazo)-2-naphthol as a specific complexing agent for the trivalent chromium’s removal from the aqueous phase to isolate hexavalent chromium compounds. The parameters influencing the extraction protocol (pH, surfactant concentration, and temperature are optimized. The obtained detection and quantification limits are 0.1 and 0.4 μg/L, respectively. The linearity is verified, with a regression coefficient close to 0.999 and the extraction recovery exceeds 99%. The method was successfully applied to analyze airborne samples collected from workplaces.     

Dual Inhibition of Pyruvate Dehydrogenase Complex and Respiratory Chain Complex Induces Apoptosis by a Mitochondria-Targeted Fluorescent Organic Arsenical in vitro and in vivo

Based on the potential therapeutic value in targeting mitochondria and the fluorophore tracing ability, a fluorescent mitochondria-targeted organic arsenical PDT-PAO-F16 was fabricated, which not only visualized the cellular distribution, but also exerted anti-cancer activity in vitro and in vivo via targeting pyruvate dehydrogenase complex (PDHC) and respiratory chain complexes in mitochondria. In details, PDT-PAO-F16 mainly accumulated into mitochondria within hours and suppressed the activity of PDHC resulting in the inhibition of ATP synthesis and thermogenesis disorder. Moreover, the suppression of respiratory chain complex I and IV accelerated the mitochondrial dysfunction leading to caspase family-dependent apoptosis. In vivo, the acute promyelocytic leukemia was greatly alleviated in the PDT-PAO-F16 treated group in APL mice model. Our results demonstrated the organic arsenical precursor with fluorescence imaging and target-anticancer efficacy is a promising anticancer drug.     

磷渣基地聚物材料固化砷钙渣的机理

以砷含量为7.63%的砷钙渣为研究对象,利用磷渣基地聚物材料对其进行固化处理,并采用毒性浸出实验考察了砷钙渣及固化体砷毒性浸出特性。结果表明:砷钙渣中砷的毒性浸出浓度可达2 450 mg/L,远超过国家毒性浸出鉴别标准限值(5 mg/L)。考察了不同养护时间、不同p H值(1~12)浸取剂环境下固化体中砷的浸出规律。结果表明:在p H=4~8范围内,砷浸出浓度较小;在酸性(p H4)和碱性(p H8)条件下砷浸出相对较大,但均小于5 mg/L。并考察了固化体中砷形态变化规律,揭示其固化机理。当养护时间为28 d时,固化体中As(Ⅲ)含量由96.3%降至28.8%,其后随着养护时间的变化固化体中As(Ⅲ)含量呈缓慢降低趋势,180 d As(Ⅲ)含量为12.6%,240 d As(Ⅲ)含量为10.8%。磷渣基地聚物固化砷钙渣机理为:磷渣基地聚物材料水化环境和所含的铁氧化物可使高毒性及强迁移性As(Ⅲ)向相对稳定的As(Ⅴ)转化;随时间的变化,磷渣基地聚物材料不断水化,并提供游离Ca2+、Al3+离子,使砷化合物经沉淀反应生成Al-As-O、Ca-As-O难溶性盐,进而降低砷浸出浓度。     

汞在MnO_x-CeO_2/γ-Al_2O_3催化剂表面的赋存形态分析

为了高效经济地控制燃煤电站汞的排放,探索新型SCR催化剂上汞的催化氧化具有重要的学术价值和广阔的应用前景。Hg0在Mn Ox-Ce O2/γ-Al2O3(Mn Ce15)催化剂上被氧化后会以多种形态存在于催化剂表面,为确定Mn Ce15催化剂上汞的化合物的赋存形态,使用程序升温热分解方法研究了纯汞化合物的分解曲线,并与在不同烟气条件下处理过的Mn Ce15催化剂的分解脱附曲线进行了对比。研究确认了反应中Hg O、Hg Cl2、Hg(NO3)2和Hg SO4的生成,并根据实验结果分析了相应的汞化合物生成的反应路径。结果表明,在模拟烟气条件下Hg Cl2是主要的异相催化反应产物,同时可以在催化剂表面检测到少量Hg O和Hg SO4的生成。这一结论可为研究SCR催化剂上Hg0的催化氧化机理提供基础。     

锡砷冶金物料中硝酸盐的直接电极电位法研究

采用离子选择性电极分析技术,在硫酸铝-硫酸银-硼酸-氨基磺酸离子强度剂体系中对锡酸钠、砷酸液等两种物料中的硝酸盐进行检测。用稀酸碱沉淀分离不大于0.80g锡酸根或25mg铁、锑、钙,200mg砷不产生干扰,硝酸盐浓度在3.23×10-5mol/L～1.61×10-2mol/L内电极响应符合能斯特方程式（斜率≥90%）,检测下限可达1.61×10-5mol/L,相对标准偏差（m=6,n=5～11）为1.44%～9.64%,加标回收率为86.0%～123.4%。     

XPS study of irreversibly adsorbed arsenic on a Pt(1 1 1) electrode

The chemical composition of an irreversibly adsorbed layer of arsenic on Pt(1 1 1) in sulfuric acid solution has been studied by X-ray photoelectron spectroscopy (XPS). From the chemical shift of the As 3d level, a change in the valence state from As(0) to As(III) with positive-going electrode potential is deduced, the total amount of As on the surface remaining constant. The As coverage derived from XPS is around 0.33 ML, which is in agreement with the charge under the current peak in the cyclic voltammogram. From the coadsorption of anions, accompanying the valence transition of As, As(III) is assumed to exist as As(OH)₃ on the surface.     

城市垃圾焚烧飞灰中重金属形态及生物有效性研究

随着集中焚烧法逐渐成为我国城市生活垃圾处理的主要方式,焚烧飞灰的安全处置与利用也成为学者普遍关注的问题。由于在填埋过程中受到各种环境要素的影响,垃圾焚烧飞灰中的重金属有可能会发生迁移和转化,重金属形态、毒性也会随之变化。本文对不同粒径城市垃圾焚烧飞灰中重金属的总量、形态及生物有效性进行了研究,为其在安全填埋及资源化利用过程中预测重金属的环境风险提供参考。     

The fate of iron during the alkali‐activation of synthetic (CaO‐)FeOx‐SiO2 slags: An Fe K‐edge XANES study

Slags from the nonferrous metals industry have great potential to be used as feedstocks for the production of alkali‐activated materials. Until now, however, only very limited information has been available about the structural characteristics of these materials. In the work presented herein, synthetic slags in the CaO–FeO_x–SiO₂ system, representing typical compositions of Fe‐rich slags, and inorganic polymers (IPs) produced from the synthetic slags by activation with alkali silicate solutions have been studied by means of X‐ray absorption near‐edge structure (XANES) spectroscopy at the Fe K‐edge. The iron in the slags was largely Fe²⁺, with an average coordination number of approximately 5 for the iron in the amorphous fraction. The increase in average oxidation number after alkali‐activation was conceptualized as the consequence of slag dissolution and IP precipitation, and employed to calculate the degrees of reaction of the slags. The degree of reaction of the slags increased with increasing amorphous fraction. The iron in the IPs had an average coordination number of approximately 5; thus, IPs produced from the Fe‐rich slags studied here are not Fe‐analogs of aluminosilicate geopolymers, but differ significantly in terms of structure from the latter.     

Solvothermal synthesis of greigite (Fe3S4)– Conducting polypyrrole nanocomposite and its application towards arsenic removal

In the present investigation, Greigite-conducting polypyrrole nanocomposite (GPPy nanocomposite) was prepared, characterized and used to remove arsenite and arsenate from aqueous solution. Fe₃S₄ was synthesized using solvothermal synthetic method and it was grafted to conducting polypyrrole matrix. The nanocomposite was characterized using FE-SEM, EDX, XRD, FTIR, TGA/DSC and BET surface area. Kinetic studies revealed that the removal process followed first order kinetics. Batch isotherm studies were performed to determine the binding capacity. Thermodynamic parameters were also computed and it indicated the spontaneous nature of the process. Electrophoretic studies were carried out to determine the point of zero charge.     

Species differentiation of chinese mollitrichosiphum (aphididae: greenideinae) driven by geographical isolation and host plant acquirement

The impact of both the uplift of the Qinghai-Tibetan Plateau (QTP) and the separation of the Taiwan and Hainan Islands on the evolution of the fauna and flora in adjacent regions has been a topic of considerable interest. Mollitrichosiphum is a polyphagous insect group with a wide range of host plants (14 families) and distributions restricted to Southeast Asia. Based on the mitochondrial Cytochrome C Oxidase Subunit I (COI) and Cytochrome b (Cytb) genes, the nuclear elongation factor-1α (EF-1α) gene, and the detailed distribution and host plant data, we investigated the species differentiation modes of the Chinese Mollitrichosiphum species. Phylogenetic analyses supported the monophyly of Mollitrichosiphum. The divergence time of Mollitrichosiphum tenuicorpus (c. 11.0 mya (million years ago)), Mollitrichosiphum nandii and Mollitrichosiphum montanum (c. 10.6 mya) was within the time frame of the uplift of the QTP. Additionally, basal species mainly fed on Fagaceae, while species that fed on multiple plants diverged considerably later. Ancestral state reconstruction suggests that Fagaceae may be the first acquired host, and the acquisition of new hosts and the expansion of host range may have promoted species differentiation within this genus. Overall, it can be concluded that geographical isolation and the expansion of the host plant range may be the main factors driving species differentiation of Mollitrichosiphum.