羧基化多壁碳纳米管对雌性小鼠卵泡发育的影响

碳纳米管(carbon nanotubes, CNTs)作为一种新形式的结晶碳,在工业及医药领域具有非常广阔的应用前景。本研究采用水溶性较好的羧基化多壁碳纳米管(MWCNTs-COOH)为研究对象,探索功能化多壁碳纳米管对小鼠卵巢发育的影响。将羧基化多壁碳纳米管溶解在含0.5% Tween-20的磷酸盐缓冲溶液(PBS)中,对实验小鼠按照2.5, 5, 10 mg·kg-1进行持续64 d的灌胃处理。处理结束后通过透射电子显微镜和HE染色观察卵巢组织的形态学变化。结果显示,碳纳米管确实进入了小鼠卵巢中。同时,随着MWCNTs-COOH暴露的增加,雌性小鼠卵泡数量显著减少,而雌性小鼠卵泡的形态结构并无明显影响。     

Fenton溶液预处理对TiO2纳米管催化活性的影响

采用Fenton溶液对TiO2纳米管电极进行预处理,研究其对TiO2纳米管催化活性的影响,考察了Fenton溶液的浓度、配比和处理时间等影响因素,研究了Fenton预处理过程中溶液中二价铁和总铁的含量变化,运用X射线光电子能谱仪(XPS)和场发射扫描电子显微镜(FESEM)对TiO2纳米管电极进行了表征,初步探讨了经处理后TiO2纳米管催化活性再生或增强的机理.结果表明,经Fenton溶液处理后的TiO2纳米管催化活性有明显地提高,Fenton溶液浓度越高,TCs降解率越大(相应于TiO2纳米管催化活性的增强);在一定浓度范围内,H2O2的配比高低对TCs降解率影响较大,其所占比例高,则降解率高,而Fe2+配比高低对TCs降解率影响相对较小.在Fenton溶液处理过程中,溶液中剩余的Fe2+含量较为恒定,总铁的含量呈下降趋势.XPS分析表明,经Fenton溶液处理后,TiO2纳米管电极表面C1s含量降低,O1s、Fe2p含量增大;部分含碳官能团含量明显降低,O1s的电子结合能向高能端位移.     

Efficient preparation of greener N-doped carbon nanotube composites for water treatment by the microwave polyol method

N-doped carbon nanotubes have unique structures and strong interactions with metal nanoparticles due to the presence of nitrogen. There is actually a need for nanoparticles to treat water, without leaching of toxic metals. Here, we synthesized nanocomposites by deposition of Ag and Fe nanoparticles on N-doped carbon nanotubes with a surface area of 52 m²/g and 2 % N content to form nanocomposites. Transmission electron microscopy (TEM) of the nanocomposites revealed that the best dispersion of the deposited nanoparticles was achieved by the microwave-assisted polyol method. The Ag and Fe nanoparticles were indeed monodispersed and uniformly distributed on the surface of the N-doped carbon nanotubes. Deposition could be achieved in 5 min. The wet impregnation and deposition–precipitation methods gave composites with agglomerated nanoparticles. We observed that leaching of Fe and Ag into water was also influenced by the preparation method. No leaching of nanoparticles was observed when the composites were prepared by the microwave polyol method. This synthesis is therefore efficient with less energy and time. The strong metal/N-doped carbon nanotube interactions render these composites suitable for use in water purification.     

Determination of total and bioaccessible metals in airborne particulate matter from an urban and a rural area at Sarajevo

Airborne particulate matter of up to 10 µm collected at an urban and a rural area at Sarajevo in 2013 and 2014 was acid digested for determination of total concentrations or extracted with synthetic gastric juice for the bioaccessible fractions of Cd, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn and determined by graphite furnace and flame atomic absorption spectrometry. The total concentrations of Cr, Cu, Fe, Mn, Pb, and V were higher at the urban site, while those of Cd, Ni, and Zn were virtually equal at both sites. The average bioaccessible fractions exhibited the following trend at both sites: Fe > Zn > Cu > Mn > Pb > Cr > V > Ni > Cd. Enrichment factors and daily intake of metals by inhalation were calculated.     

Heavy Metals in Superficial Sediments from the Ligurian Sea, Italy

In this paper we are presenting the concentrations and the distributions of trace metals (Fe, Ni, Cr, Cu, Pb and Zn) in the coastal area of the Ligurian Sea between Capo Noli and Capo Mele. Fifty-six samples were subjected to textural, organic carbon and chemical analyses. Three different extraction methods were used: 1N NH₂OH.HCl plus 25% CH₃COOH, nitric acid solution, and total attack with HClO₄-HF mixture. The solutions were analysed by atomic absorption spectrophotometry. The results obtained confirm that the extraction methods which are most informative for environmental purposes are the cold or the easily extractable metal techniques. The results also show that for the study area the concentrations of Fe, Ni, Cr, Cu, Pb, and Zn do not indicate traces of anthropogenic inputs.     

Nanofertilizers and nanopesticides for agriculture

The excess use of mineral fertilizers and unsafe pesticides has led to pollution and serious health issues. Nanoscience may solve those issues by providing nanomaterials of higher performance. Here we reviewed the development of nanofertilizers and nanopesticides and their applications on crop systems. Nanofertilizers such as N, P, K, Fe, Mn, Zn, Cu, Mo and carbon nanotubes show better release and targeted delivery efficiency. Nanopesticides such as Ag, Cu, SiO₂, ZnO and nanoformulations show better broad-spectrum pest protection efficiency in comparison with conventional pesticides.     

Lichtallergien und andere Lichtempfindlichkeitsreaktionen

Adverse reactions of the skin to light comprise a number of different dermatologic conditions. In light-‘allergies’ in the narrower sense non-ionised electromagnetic radiation (ultraviolet (UV)-A/-B radiation or visible light) provokes an immunologic or allergic skin reaction. These include solar urticaria, an, immunoglobulin E-mediated, immediate-type allergic photoreaction, photoallergic contact dermatitis and photoallergic (drug) exanthema, which are cell-mediated, delayed-type allergic photoreactions due to photosensitization, chronic actinic dermatitis and polymorphic light eruption. Beyond it there are nonimmunologic photosensitive and photoaggravated skin diseases, like exogenous and endogenous phototoxicity, xeroderma pigmentosum, which is based on a genetic defect, or the autoimmune disease lupus erythematosus.     

2种类型多壁碳纳米管对蛋白核小球藻的毒理研究

碳纳米材料由于其具有优异的性能,得以广泛生产和使用,其不可避免会进入水环境中,对水生生态系统造成潜在影响。多壁碳纳米管(P-MWCNTs)和羟基化多壁碳纳米管(MWCNTs-OH)作为纳米材料的典型代表,应用非常广泛,其潜在的环境效应受到人们越来越多的关注。为此,本文以蛋白核小球藻(Chlorella pyrenoidosa)作为受试生物,通过暴露实验,研究了P-MWCNTs和MWCNTs-OH对蛋白核小球藻的生物学效应。研究结果表明：1)当P-MWCNTs浓度≤10 mg·L-1、MWCNTs-OH≤20 mg·L-1浓度时对蛋白核小球藻生长未造成影响;2)暴露96 h后,当P-MWCNTs≤10 mg·L-1、MWCNTs-OH浓度≤20 mg·L-1时,蛋白核小球藻细胞可溶性蛋白质含量增加,当P-MWCNTs浓度≥20 mg·L-1、MWCNTs-OH浓度≥40 mg·L-1时,2种类型MWCNTs均对蛋白核小球藻造成毒性效应;3)随着2种类型MWCNTs浓度的增加,蛋白核小球藻细胞总抗氧化能力(T-AOC)值减少,蛋白核小球藻细胞丙二醛(MDA)含量显著增加,细胞的健康程度逐渐恶化,细胞结构受到严重损伤;4)MWCNTs-OH比P-MWCNTs具有更好的生物相容性。     

Heavy Metals in Superficial Sediments from the Ligurian Sea,Italy

In this paper we are presenting the concentrations and the distributions of trace metals (Fe, Ni, Cr, Cu, Pb and Zn) in the coastal area of the Ligurian Sea between Capo Noli and Capo Mele. Fifty-six samples were subjected to textural, organic carbon and chemical analyses. Three different extraction methods were used: 1N NH₂OH.HCl plus 25% CH₃COOH, nitric acid solution, and total attack with HClO₄-HF mixture. The solutions were analysed by atomic absorption spectrophotometry. The results obtained confirm that the extraction methods which are most informative for environmental purposes are the cold or the easily extractable metal techniques. The results also show that for the study area the concentrations of Fe, Ni, Cr, Cu, Pb, and Zn do not indicate traces of anthropogenic inputs.     

甲醛暴露时间延长加剧小鼠哮喘模型肺氧化损伤并促进IL-17表达

为了探究不同暴露时间甲醛对小鼠哮喘模型肺氧化应激及IL-17表达的影响,用浓度为3.0 mg·m~(-3)的甲醛气体吸入染毒,同时将48只雄性Balb/c小鼠随机分为6组:(1)对照组(生理盐水组);(2)ovalbumin(OVA)致敏组;(3)0.5 h甲醛+OVA组;(4)1h甲醛+OVA组;(5)1.5 h甲醛+OVA组;(6)2 h甲醛+OVA组,以不同时间长度进行甲醛暴露,连续35 d。OVA致敏组、0.5 h甲醛+OVA组、1 h甲醛+OVA组、1.5 h甲醛+OVA组、2 h甲醛+OVA组均在第11、18及25天腹腔注射OVA致敏液(5 mg OVA+175 mg Al(OH)_3+30 mL生理盐水),第29~35天(共计1周)进行1%OVA雾化(30 min·d~(-1)),每日1次,诱发哮喘。第36天进行以下操作:取肺组织测定肺系数并制作肺匀浆,检测肺组织中活性氧自由基(ROS)、丙二醛(MDA)和还原型谷胱甘肽(GSH)的含量,并采用ELISA法检测肺组织中IL-17的水平。同时,采用HE染色法观察小鼠肺部气道的病理学变化。结果显示,在浓度为3.0 mg·m~(-3)的甲醛气体吸入染毒条件下,与对照组相比,1.5 h甲醛+OVA染毒组、2 h甲醛+OVA染毒组ROS、MDA、IL-17含量上升,具有统计学意义(P0.01)。同时,随着暴露时间长度的增加,小鼠肺部气道出现明显病理学变化。综上所述,每天2 h甲醛+OVA染毒能对小鼠肺造成损伤并恶化OVA对小鼠肺的损伤,产生炎症反应,并通过氧化应激反应介导。     

Self-catalytic pyrolysis thermodynamics of waste printed circuit boards with co-existing metals

● The co-existing metals in WPCBs has positive catalytic influence in pyrolysis. ● Cu, Fe, Ni can promote reaction progress and reduce the apparent activation energy. ● Ni play better role in promoting WPCB pyrolysis reaction. Waste printed circuit boards (WPCBs) are generated increasingly recent years with the rapid replacement of electric and electronic products. Pyrolysis is considered to be a potential environmentally-friendly technology for recovering organic and metal resources from WPCBs. Thermogravimetric analysis and kinetic analysis of WPCBs were carried out in this study. It showed that the co-existing metals (Cu, Fe, Ni) in WPCBs have positive self-catalytic influence during the pyrolysis process. To illustrate their catalytic effects, the apparent activation energy was calculated by differential model. Contributions of different reactions during catalytic pyrolysis process was studied and the mechanism function was obtained by Šesták-Berggren model. The results showed that Cu, Fe, Ni can promote the reaction progress and reduce the apparent activation energy. Among the three metals, Ni plays better catalytic role than Cu, then Fe. This work provides theoretical base for understanding the three metals’ catalytic influence during the pyrolysis of non-metal powders in WPCBs.     

Study of sorptive properties of trap systems for selective enrichment of volatile organic compounds from tobacco smoke samples

There is a dearth of data on the consumer product concentrations of iron, lead, and nickel for accurate comparison to be made. The levels of these elements were determined in 85 samples of six different classes of personal care products commonly used in Nigeria using atomic absorption spectrophotometry. The results of the analysis showed that the range of the mean concentrations of Fe was 0.485–1.108 ppm, Pb ND–0.163 ppm, and Ni ND-0.160 ppm. The analytical data have demonstrated that the selected consumer products are possible sources of iron, lead, and nickel exposure. Users can be exposed to these metals directly through dermal contact or inhalation. The regulations relating to cosmetic products give no limit values for heavy metals in cosmetic products, hence, it was difficult to establish if the values obtained in this study are safe or not. Prolonged use of soaps, creams, and detergent containing these elements may pose threat to human health and the environment. This could be responsible for various skin diseases such as allergic skin, follicular and pigmentary disorders, which are common among the users (exposed groups) of these products in Nigeria. A body of evidence has presented a rare example of systemic allergic dermatitis caused by topical application of a mercury-containing cosmetic to the upper lip of a 32-year-old Turkish patient.     

Metal partitioning in sediment pore water from the Ondo coastal region,Nigeria

Distribution and equilibrium partitioning of metals (Cd, Cu, Cr, Fe, Ni, Pb, Mn, and Zn) between pore water and surface sediments at the Ilaje coast of Ondo State, Nigeria, were studied. The Ilaje River can be one of the interesting research locations because of its economic nature and history of oil pollution. Seasonal variations were observed to investigate possible variations in the availability of metals for organisms throughout the year. The concentrations in both sediments and pore water during the dry and wet seasons were as follows: Cu?>?Fe???Mn?>?Pb?>?Ni?>?Cr?>?Cd?>?Zn. The pore water–sediment partition coefficient (K _p) showed that Zn and Cd were highly mobile while Fe and Cu have restricted mobility. Dissolved organic carbon (DOC) in pore water had a strong influence on mobility and bioavailability of all the metals (p?K _oc), increased levels of Fe and Cu were linked to lithological origin. Concentrations of Pb and Ni were associated with petroleum-related sources. The significance of the field-based techniques for ecotoxicological purposes is discussed.     

International standardized procedures for in vivo evaluation of multi-walled carbon nanotube toxicity in water

The classical approach in ecotoxicological evaluation of chemical substances consists of conducting standardized bioassays on organism models. In this work, the potential impact of industrial multi-walled carbon nanotubes was investigated by ecotoxicological standardized procedures using aquatic organisms of different trophic levels, namely bacteria, green algae, invertebrates, fish, and amphibians. The results indicated (1) inhibition of growth in amphibians at 50 mg L^?1 and higher, and (2) no effects on daphnia and fish up to 100 mg L^?1. With the exception of algae (for which Fe deficiency is measured), it seems that the observed toxicity may be due to physiological effects in relation to the ingestion of carbon nanotubes not necessarily related to their intrinsic effects.     

多壁碳纳米管对小鼠肺脏和肝脏组织SOD活力和GSH含量的影响

为了研究多壁碳纳米管(MWCNTs)对小鼠肺脏和肝脏组织抗氧化系统的影响,将20只雄性昆明小鼠随机分成4组,采用腹腔注射进行一次性染毒,其中3个染毒组分别腹腔注入0.1、0.2、0.4mg·mL-1的多壁碳纳米管(粒径20～40nm)悬液1mL,对照组注入等体积生理盐水,染毒5d后测定肺脏和肝脏组织匀浆中超氧化物歧化酶(SOD)活力、还原型谷胱甘肽(GSH)含量.结果表明,随着多壁碳纳米管染毒浓度的升高,小鼠肺脏和肝脏组织SOD活力、GSH含量均呈逐渐降低趋势;在实验浓度(0～0.4mg·mL-1)下,SOD活力、GSH含量与多壁碳纳米管染毒浓度呈明显的剂量-效应关系.以上结果表明多壁碳纳米管对小鼠肺脏和肝脏抗氧化系统具有一定程度的抑制作用。     

Speciation of particulate trace metals in sediments of Anarbe reservoir∗

Total concentration and chemical forms of heavy metals in samples of sediment from a drinking water reservoir have been analysed. The result of total metal contest shows Fe and Mn concentration increase along the reservoir, from 4.4% in Fe and 0.07% in Mn in the end part to 6.4% Fe and 0.22% Mn at the dam. However, a decrease in organic matter along the reservoir is observed. In order to test the accuracy of the digestion methods used, a standard reference material was also analysed.

Trace metal concentrations, with exception of Cadmium, Pb and Mn, found in fraction 5 are higher than those observed in the others extractions, Fe, Ni, Zn, Cr and Cu content in non‐residual fraction is found mainly in moderately reducible fraction, but the percentage of this fraction in each metal is very different.     

High-valent iron-based oxidants to treat perfluorooctanesulfonate and perfluorooctanoic acid in water

Perfluoroalkyl and polyfluoroalkyl substances are occurring in consumer and industrial products. They have been found globally in the aquatic environment including drinking water sources and treated wastewater effluents, which has raised concern of potential human health effects because these substances may be bioaccumulative and extremely persistent. The saturated carbon–fluorine bonds of the substances make them resistant to degradation by physical, chemical, and biological processes. There is therefore a need for advanced remediation methods. Iron-based methods involving high-valent compounds are appealing to degrade these substances due to their high oxidation potentials and capability to generate environmentally friendly by-products. This article presents for the first time the oxidation ability of tetraoxy anions of iron(V) (Fe^VO₄ ^3?, Fe(V)), and iron(IV) (Fe^IVO₄ ^4?, Fe(IV)), commonly called ferrates, in neutral and alkaline solutions. Solid compounds of Fe(V) (K₃FeO₄) and Fe(IV) (Na₄FeO₄) were added directly into buffered solution containing perfluorooctansulfonate and perfluorooctanoic acid at pH 7.0 and 9.0, and mixed solutions were subjected to analysis for remaining fluoro compounds after 5 days. The analysis was performed by liquid chromatography–mass spectrometry/mass spectrometry technique. Fe(IV) showed the highest ability to oxidize the studied contaminants; the maximum removals were 34 % for perfluorooctansulfonate and 23 % for perfluorooctanoic acid. Both Fe(V) and Fe(IV) had slightly higher tendency to oxidize contaminants at alkaline pH than at neutral pH. Results were described by invoking reactions involved in oxidation of perfluorooctansulfonate and perfluorooctanoic acid by ferrates in aqueous solution. The results demonstrated potentials of Fe(V) and Fe(IV) to degrade perfluoroalkyl substances in contaminated water.     

Plants growing in a mining area: screening for metal accumulator plants possibly useful for bioremediation

A field study was conducted in an iron mine in Hamedan (Iran) to find native accumulator plants and to evaluate the extent of metal bioaccumulation in the naturally growing vegetation. The concentrations of total As, Cd, Cr, Fe, Mn, Mo, Ni, Pb, Si, and Zn were found to be higher in the mine than in soil. These plants accumulated the highest amounts of the following metals in their roots: Euphorbia cheiradenia As, Stipa barbata Cd, Pb and Cr, Euphorbia macroclada Cu, Centaurea iberica Fe, Reseda lutea Mo, Salvia spinosa Ni and Zn, and Xanthium strumarium Se. In the aerial parts, the highest metal accumulation was found in Epilobium fragilis As, Carthamus oxyacantha Cd, Fe, Mn, and Pb, Verbascum speciosum Cu, Centaurea iberica Mo, Salvia spinosa Ni and Cr, Glaucium grandiflorum Se, and Malva neglecta Zn. Enrichment factors and bioconcentration factors were also determined; C. oxyacantha, S. spinosa, M. neglecta, C. iberica, V. speciosum, G. grandiflorum, and E. fragilis are the most effective accumulators and are proposed for phytoremediation of polluted soils.     

Concentrations of some elements in the sediments of a river in Anhui Province,China

A total of 49 sediment samples from New Bian River near the city of Suzhou in northern Anhui Province, China, were analyzed by inductively coupled plasma-mass spectrometry for As, Cr, Pb, Cu, Fe, Zn, Mn, and Ni. Geoaccumulation indices (I_geo) were used to assess the influence of human activities. Correlation analysis and principal component analysis were also performed. The geoaccumulation indices were in the order of As > Cu > Cr > Ni > Mn > Zn > Pb > Fe, the first four of which had values above 0.5. We considered New Bian River to be moderately contaminated with As, Cr, Cu, and Ni. Correlation analysis and principal component analysis indicated that the presence of Fe, Cu, Ni, Mn, Zn, and Pb in New Bian River was caused by soil or rock weathering, whereas the elevated levels of As and Cr depended upon urban, agricultural, and industrial factors. The sampling stations around the towns were dominated by Component 2 (As and Cr), and the sampling stations that distributed along New Bian River were dominated by Component 1 (Fe, Cu, Ni, Mn, Zn, and Pb).     

铁氧体—高压水解一步除氰,镍的机理研究

本文研究了在１．０１３ＭＰａ，１８０℃条件下，废水中ＣＮ＾－，ＮＨ３，Ｎｉ＾２＋并存时，以形成铁氧体同时进行高压水解一步除氰，除镍的反应机理。结果发现，镍铁氧体的形成是由于镍离子取代了Ｆｅ３Ｏ４中的两价铁的晶格位置形成的，新生太的Ｆｅ３Ｏ４具有表面吸附作用，但随着反应时间的延长吸附量会有所下降；氰水解是镍形成铁氧体的前提，为含氰、含镍废水在高压水解条件下铁氧体一步法治理奠定了理论基础。