Heavy metal contamination in the vicinity of an industrial area near Bucharest

BACKGROUND, AIMS AND SCOPE: Chromium enters into the aquatic environment as a result of effluent discharge from steel works, electroplating, leather tanning industries and chemical industries. As the Cr(VI) is very harmful to living organisms, it should be quickly removed from the environment when it happens to be contaminated. Therefore, the aim of this laboratory research was to develop a rapid, simple and adaptable solvent extraction system to quantitatively remove Cr(VI) from polluted waters. METHODS: Aqueous salt-solutions containing Cr(VI) as CrO4(2-) at ppm level (4-6 ppm) were prepared. Equal volumes (5 ml) of aqueous and organic (2-PrOH) phases were mixed in a 10 ml centrifuge tube for 15 min, centrifuged and separated. Concentrations of Cr(VI), in both the aqueous and organic phases, were determined by atomic absorption spectrometry. The effects of salt and acid concentrations, and phase-contact time on the extraction of Cr(VI) were investigated. In addition, the extraction of Cr(VI) was assessed in the presence of tetramethylammonium chloride (TMAC) in 2-PrOH phase. Effects of some other metals, (Cd(II), Co(II), Cu(II), Ni(II) and Zn(II)), on the extraction of Cr(VI) were also investigated. RESULTS AND DISCUSSION: The Cr(VI) at ppm level was extracted quantitatively by salting-out the homogeneous system of water and 2-propanol(2-PrOH) using chloride salts, namely CaCl2 or NaCl, under acidic chloride media. The extracted chemical species of Cr(VI) was confirmed to be the CrO3Cl-. The ion-pair complex extracted into the organic phase was rationalized as the solvated ion-pair complex of [2-PrOH2+, CrO3Cl-]. The complex was no longer stable. It implied the reaction between extracted species. Studies revealed that salts and acid directly participated in the formation of the above complex. Use of extracting agents (TMAC) didn't show any significant effect on the extraction of Cr(VI) under high salting-out conditions. There is no significant interference effect on the extraction of Cr(VI) by the presence of other metals. The Cr(VI) in the organic phase was back-extracted using an aqueous ammonia solution (1.6 mol dm(-3)) containing 3 mol dm(-3) NaCl. The extraction mechanism of Cr(VI) is also discussed. CONCLUSIONS: Salting-out of homogeneous mixed solvent of 2-propanol can be employed to extract Cr(VI) quantitatively, as an ion-pair of [2-PrOH2+ * CrO3Cl-] solvated by 2-PrOH molecules. Then, the complex becomes 'solvent-like' and is readily separated into the organic phase. The increase of Cl- ion concentration in the aqueous phase favors the extraction. The 2-PrOH, salts and acid play important roles in the extraction process. There is no need to use an extracting agent at a high salting-out condition. RECOMMENDATIONS AND PERSPECTIVES: Chromium(VI) must be quickly removed before it enters into the natural cycle. As the 2-PrOH is water-miscible in any proportion, ion-pairing between 2-PrOH2+ and CrO3Cl- becomes very fast. As a result, Cr(VI) can easily be extracted. Therefore, the method is recommended as a simple, rapid and adaptable method to quickly separate Cr(VI) from aqueous samples.     

Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

大气CO2浓度增高对不同供氮水平下水稻生长和化感物质释放的影响

利用开放式空气CO2浓度升高(free air carbon-dioxide enrichment,FACE)平台中的水培试验,研究了低氮(LN:10 mg·L-1)和高氮(HN:30 mg·L-1)水平下,大气CO2浓度升高对化感与非化感水稻(Oryza sativa L.)品种的生长、碳氮比(C/N)和化感物质含量的影响,并分析了CO2浓度升高条件下水稻C/N和化感物质含量间的相互关系.结果表明:CO2浓度升高对化感(PI)与非化感水稻品种(秀水)的生长均有极显著促进作用.CO2浓度升高后,LN条件下水稻C/N显著增加,HN条件下则无显著变化.CO2浓度升高后化感水稻品种次生代谢物质含量增加,特征化感物质含量增加,非化感品种的这种变化不显著.化感水稻品种C/N分别与次生代谢物质含量和特征化感物质含量之间呈显著正相关关系.     

铝合金微电偶腐蚀机理与数值模拟研究进展

综述了铝合金微电偶腐蚀在机理研究和数值模拟两方面的研究进展,针对独立微电偶的腐蚀机理表征、多元微电偶空间随机分布相互作用规律、结构/载荷因素与铝合金微电偶腐蚀驱动力间的竞争机制等3个方面进行了展望,期望为铝合金微电偶腐蚀研究提供方向参考。     

负载型纳米TiO2光催化剂的制备及其降解水中微量间二甲苯的研究

采用浸涂-烧结法制备的纳米TiO2光催化剂负载量约为6mg／g载体，催化剂经5次重复使用其催化效果稳定，表明催化剂表面TiO2粉体负载牢固；以高压汞灯为光源，对水中微量间二甲苯的负载型纳米TiO2光催化氧化过程的研究表明：初始浓度在6．68～17．36mg／L的范围内，间二甲苯的光催化反应遵循表现一级反应动力学规律，反应的表现速率常数随溶液初始浓度的增大而减小，半衰期则随初始浓度的增大而增加。     

微囊藻毒素LR对BRL-3A凋亡相关蛋白表达的影响

用蛋白印迹法研究了微囊藻毒素LR(MCLR)暴露时大鼠BRL-3A细胞p53、Bcl-2和Bax的表达情况.结果表明,与对照组相比,各实验组p53和Bax表达均明显升高.除了10nmol/L LR暴露1h实验组外,其它实验组Bcl-2表达均下降.在低浓度组(10nmol/L),随暴露时间的延长,p53和Bax表达逐渐升高,Bcl-2表达逐渐下降,而在中浓度(100nmol/L)和高浓度组(1000nmol/L),蛋白表达与暴露时间的一致性没有低浓度组(10nmol/L)明显.表明p53、Bcl-2和Bax在MCLR诱导的细胞凋亡中可能起重要作用.     

Cu2+强化UV活化过氧乙酸降解水中的双氯芬酸

研究了Cu²⁺强化UV活化过氧乙酸（Cu²⁺/UV/PAA）对水中双氯芬酸（DCF）的降解,考察了pH值、PAA投加量、Cu²⁺投加量、无机阴离子（Cl^-、SO₄^2-、NO₃^-和CO₃^2-）和溶解有机物（DOM）对DCF去除的影响;探讨了DCF在该体系中的降解产物和转化机理.结果表明：UV和Cu²⁺都能活化PAA产生活性自由基促进DCF降解.DCF在Cu²⁺/UV/PAA中的降解遵循准一级动力学,其降解可能归因于直接光解、HO^·氧化和CH₃COO^·、CH₃COOO^·等其它自由基氧化.在pH=3~11范围内,DCF降解的最佳pH=8.5.DCF的降解效率随着PAA投加量的增大而逐渐增高,过量的PAA能与DCF竞争HO^·.Cu²⁺用量的提高也能促进DCF的去除,但是过量的Cu²⁺可生成Cu（OH）₂导致其催化能力下降.由于NO₃^-在UV照射下可以产生HO^·,其对DCF降解有促进作用,且NO₃^-浓度越高,促进作用越明显.不同浓度的Cl^-、SO₄^2-、CO₃^2-和DOM对DCF降解影响较小.在Cu²⁺/UV/PAA降解DCF的过程中,共检测出13种降解产物.根据这些降解产物,提出了DCF可能的转化机理,包括8种不同的反应路径.     

南海高温高压含CO2气井管柱腐蚀适用性评价

目的 明确南海高温高压含CO2气井管柱材料腐蚀适用性,指导现场管柱材料选择.方法 采用高温高压釜腐蚀实验仪器对井筒高温高压环境条件下不同材料腐蚀速率进行实验分析,并采用扫描电镜及能谱分析仪对腐蚀实验后试样腐蚀形貌进行分析,评价不同井筒环境下管柱材料腐蚀适用性.结果 150℃条件下,材料腐蚀速率随分压的增加而增大,同时随...     

半岛型城市PM2.5多情景数值模拟研究

烟台是中国最东部半岛型城市之一,研究应用WRF-CMAQ空气质量模拟系统和排放清单技术,建立以PM2.5质量改善为核心的一次污染物质减排情景和PM2.5浓度下降之间的定量对应关系.分析结果表明,若烟台2020年实现空气质量达标,SO2、NOx、一次PM2.5分别需消减30%、30%和40%以上;一次PM2.5减排控制对PM2.5浓度下降的贡献,是SO2和NOx等常规污染物减排控制效益的8倍左右;如果仅依靠消减SO2和NOx等常规污染物,无法实现PM2.5浓度的大幅度下降.     

厌氧水环境中噬菌体MS2的存活和团聚特性及理化因素的影响

为探究病毒在厌氧水环境中的存活特性,以噬菌体MS2为模式病毒,采用双层平板法进行噬菌体MS2的定量检测,研究温度、pH值、悬浮颗粒物、乙酸等理化条件对噬菌体MS2的影响,分析其衰减动力学特征,并通过测定Zeta电位和噬菌斑直径考察噬菌体颗粒在不同条件下的聚集状况.结果表明,在厌氧水环境中,噬菌体MS2的衰减符合一阶指数衰减模型.在众多研究因素中,温度是影响噬菌体MS2存活的最主要因素.噬菌体MS2在4,17,25和35℃时的T₉₀分别为20.36,6.14,5.15和0.46d.35℃条件下12h后噬菌体失活率高达2.44lg,而4℃条件下7d后噬菌体失活率仅有0.78lg.增加乙酸浓度能明显提高噬菌体MS2的衰减速率.低pH值和悬浮颗粒物条件会促进噬菌体的团聚,使噬菌体颗粒Zeta电位降低,水力学直径增大,但悬浮颗粒物浓度过高会影响颗粒间的静电作用.噬菌体的团聚也增加了噬菌斑的直径,pH=6和20mg/L的悬浮颗粒物条件下,直径1.0mm以上的大噬菌斑数量占比分别达到了45.61%和57.74%.明确厌氧水环境中各种理化因素对噬菌体MS2的影响,可为水环境病毒控制提供科学依据.