预处理方式对氧化-还原联合技术修复硝基苯污染地下水的影响

为了探究氧化与还原预处理对氧化-还原联合技术修复硝基苯污染地下水的影响,选取2,4-DNT（2,4-二硝基甲苯）为研究对象,构建过硫酸盐/铁炭修复技术体系,分别设置2个试验槽,一个试验槽以过硫酸盐作为氧化预处理联合以铁炭作为还原后处理,另一个试验槽以铁炭作为还原预处理联合以过硫酸盐作为氧化后处理,对比研究构建的氧化-还原联合系统中不同氧化与还原预处理方式对2,4-DNT去除机制的影响.结果表明:①过硫酸盐氧化材料填充位置显著影响试验槽pH和ORP（氧化还原电位）的变化,在运行周期5 PV（PV为孔隙体积,1 PV时间约为4 h）内,pH可显著增至11左右,ORP值达到最高.②在运行周期5 PV内,氧化填充层S₂O₈2-浓度和还原填充层Fe2+浓度均显著降低.③在运行周期5 PV内,随运行周期的增加,以过硫酸盐作为氧化预处理联合以铁炭作为还原后处理的协同技术体系对2,4-DNT的去除效果显著降低,以铁炭作为还原预处理联合以过硫酸盐作为氧化后处理的协同技术体系对2,4-DNT的去除率维持在100%.④通过液相-质谱联用技术,识别构建的氧化-还原联合技术体系内2,4-DNT降解的主要中间产物,同时结合铁炭微电解还原机制和过硫酸盐氧化机制提出了2,4-DNT协同处理机制及其可能的降解路径.研究显示,还原预处理更有利于氧化-还原联合技术对地下水中2,4-DNT的去除,可为有效处理硝基苯化合物污染地下水提供理论支撑.      

Multiresidue determination and potential risks of emerging pesticides in aquatic products from Northeast China by LC–MS/MS

A simple method for determining 33 pesticides with a wide polarity range(log Kow0.6-4.5) in aquatic products was developed based on LC–MS/MS. The target analytes included three types of widely used pesticides: insecticides, fungicides and herbicides. Based on the optimization of ultrasonic assisted extraction and GPC clean-up procedures, the matrix effect, extraction recoveries and LOD were improved distinctively. LOQ of this method was below 0.5 ng/g for all pesticides, which is superior to values in the literature, and the matrix effect was reduced effectively(-14.7% to 7.5%). The method was successfully applied to investigate the pesticide residue levels of twenty-five samples including seven common kinds of fishes from Northeast China. The results showed that all targeted pesticides were present in the fish samples; however, their levels were low, except for atrazine, linuron,ethoprophos, tetrachlorvinphos, acetochlor and fenthion. Atrazine and linuron caught our attention because the concentrations of atrazine in fish samples from Liaoning province were in the range of 0.5-8 ng/g(w/w) with mean concentration of 2.3 ng/g, which were far above those of other pesticides. The levels of linuron were in the range of 0.6-6 ng/g(mean concentration 2.8 ng/g), which were the highest among all targeted pesticides in the Inner Mongolia. This is the first systematic investigation on the characteristics and levels of these pesticides in aquatic products from northeast China. Considering their toxicity and bioaccumulation, the potential risk of atrazine and linuron from consuming aquatic products should be paid more attention.     

Observations of atmospheric pollutants at Lhasa during 2014–2015: Pollution status and the influence of meteorological factors

Atmospheric pollutants including SO₂, NO₂, CO, O₃ and inhalable particulate matter (PM_2.5 and PM₁₀) were monitored continuously from March 2014 to February 2015 to investigate characteristics of air pollution at Lhasa, Tibetan Plateau. Species exhibited similar seasonal variations except O₃, with the peaks in winter but low valleys in summer. The maximum O₃ concentration was observed in spring, followed by summer, autumn, and winter. The positive correlation between O₃ and PM₁₀ in spring indicated similar sources of them, and was assumed to be turbulent transport. Temperature was the dominant meteorological factor for most species in spring. High temperature accelerates O₃ photochemistry, and favors air disturbance which is conductive to dust resuspension in spring. Relative humidity (RH) and atmospheric pressure were the main meteorological factors in summer. RH showed negative correlations with species, while atmospheric pressure posed opposite situation. Wind speed (WS) was the dominant meteorological factor in autumn, the negative correlations between WS and species indicated diffusion by wind. Most species showed non-significant correlations with meteorological factors in winter, indicating the dependence of pollution on source emission rather than restriction by meteorology. Pollution weather character indicated that emissions were from biomass burning and dust suspension, and meteorological factors also played an important role. Air stream injection from the stratosphere was observed during O₃ pollution period. Air parcels from Southwest Asia were observed during air pollution period in winter. An enhancement in air pollutants such as O₃ would be expected in the future, more attention should be given to countermeasures for prevention of air pollution in the future.     

Inhibition of thrombin by functionalized C60 nanoparticles revealed via in vitro assays and in silico studies

The studies on the human toxicity of nanoparticles (NPs) are far behind the rapid development of engineered functionalized NPs. Fullerene has been widely used as drug carrier skeleton due to its reported low risk. However, different from other kinds of NPs, fullerene-based NPs (C₆₀ NPs) have been found to have an anticoagulation effect, although the potential target is still unknown. In the study, both experimental and computational methods were adopted to gain mechanistic insight into the modulation of thrombin activity by nine kinds of C₆₀ NPs with diverse surface chemistry properties. In vitro enzyme activity assays showed that all tested surface-modified C₆₀ NPs exhibited thrombin inhibition ability. Kinetic studies coupled with competitive testing using 3 known inhibitors indicated that six of the C₆₀ NPs, of greater hydrophobicity and hydrogen bond (HB) donor acidity or acceptor basicity, acted as competitive inhibitors of thrombin by directly interacting with the active site of thrombin. A simple quantitative nanostructure-activity relationship model relating the surface substituent properties to the inhibition potential was then established for the six competitive inhibitors. Molecular docking analysis revealed that the intermolecular HB interactions were important for the specific binding of C₆₀ NPs to the active site canyon, while the additional stability provided by the surface groups through van der Waals interaction also play a key role in the thrombin binding affinity of the NPs. Our results suggest that thrombin is a possible target of the surface-functionalized C₆₀ NPs relevant to their anticoagulation effect.     

Mercury in soil, vegetable and human hair in a typical mining area in China: Implication for human exposure

Concentrations of total mercury(T-Hg) and methylmercury(MeHg) in soil, vegetables, and human hair were measured in a mercury mining area in central China. T-Hg and MeHg concentrations in soil ranged from 1.53 to 1054.97 mg/kg and 0.88 to 46.52 μg/kg, respectively.T-Hg concentrations was correlated with total organic carbon(TOC) content(R~2= 0.50, p0.01)and pH values(R~2= 0.21, p0.05). A significant linear relationship was observed between MeHg concentrations and the abundance of sulfate-reducing bacteria(SRB)(R~2= 0.39, p0.05) in soil.Soil incubation experiments amended with specific microbial stimulants and inhibitors showed that Hg methylation was derived from SRB activity. T-Hg and MeHg concentrations in vegetables were 24.79 – 781.02 μg/kg and 0.01 – 0.18 μg/kg, respectively; levels in the edible parts were significantly higher than in the roots(T-Hg: p0.05; MeHg: p0.01). Hg species concentrations in rhizosphere soil were positively correlated to those in vegetables(p0.01), indicating that soil was an important source of Hg in vegetables. Risk assessment indicated that the consumption of vegetables could result in higher probable daily intake(PDI) of T-Hg than the provisional tolerable daily intake(PTDI) for both adults and children. In contrast, the PDI of MeHg was lower than the reference dose. T-Hg and MeHg concentrations in hair samples ranged from 1.57 to 12.61 mg/kg and 0.04 to 0.94 mg/kg, respectively, and MeHg concentration in hair positively related to PDI of MeHg via vegetable consumption(R~2= 0.39, p0.05), suggesting that vegetable may pose health risk to local residents.     

Characterization and acid-mobilization study for typical iron-bearing clay mineral

In this study, iron speciation in five standard clay samples was characterized. Iron mobilization from these clays was then measured in acidic media. For comparison, a commercially available Arizona test dust (ATD) was also observed. The results showed that the free-Fe contents of clays were commonly lower than that of dust aerosols. The components of clays were dominant by the structural Fe held in the aluminosilicate lattice. The iron solubility of the clays were in the order of KGa-2?>?SWy-2?>?CCa-2?>?IMt-2?>?NAu-2. Based upon the Mössbauer spectrum and transmission electron microscopy (TEM) analysis, the Fe(II) fraction and the Fe/Si ratio of clay particles changed after dissolution, suggesting the total Fe solubility depended on the Fe atom states existing within the aluminosilicate lattice. The Fe in KGa-2 and SWy-2 was most likely substituted for alkaline elements as the interlayer ions held by ionic bonds in the aluminosilicate, which are more liable to dissolution. However, the Fe in NAu-2 was more likely to be bound by strong covalent bonds in aluminosilicate mineral, which is less soluble. The much highly soluble Fe in ATD was not only linked to the dissolution of an appreciable fraction of Fe(II), but also could be attributed to the fact that the Fe bonds in the clay fraction of ATD were mainly present as ionic bonds. The TEM images showed that reacted clay particles displayed less aggregate particles, with nanoparticle aggregates and the Fe/S-rich tiny particles attached to the remains.     

Characteristics of the pollutant emissions in a tunnel of Shanghai on a weekday

Tunnel displays a typical semi-closed environment, and multitudes of the pollutants tend to accumulate. The samples of gaseous pollutants and particulate matter(PM) were collected from the Xiangyin tunnel at Shanghai to investigate the characteristics of the pollutant emissions. The results indicated that both gaseous pollutants and PM exhibited much higher concentrations during the rush hours in the morning and at night due to vehicle emission. Two peaks of the PM concentration were observed in the scope of 0.7‐1.1 and 3.3–4.7 μm, accounting for 14.6% and 20.3% of the total concentrations, respectively.Organic matter(OM), EC, and many water-soluble ions were markedly higher at the rush hours in the morning than those at night, implicating comprehensive effects of vehicle types and traffic volume. The particle number concentrations exhibited two peaks at Aitken mode(25 nm and 100 nm) and accumulation mode(600 nm), while the particle volume concentration displayed high values at the accumulation mode(100–500 nm) and coarse mode(2.5–4.0 μm). The peak around 100 nm was detected in the morning rush hours, but it diminished with the decrease of the traffic volume. Individual-particle analysis revealed that main particles in the tunnel were Fe-rich particles, K-rich particles, mineral particles,Ca–S rich particles and Al–Si particles. The particles collected at the rush hours displayed marked different morphologies, element concentrations and particle sizes compared to the ones collected at the non-rush period. The data presented herein could shed a light on the feature of vehicle emissions.     

舟山群岛海域资源开发利用研究

舟山群岛是我国第一大群岛,自然资源丰富,区位条件优越。本文分析了舟山海域资源特征、优势及资源开发利用的限制因素,对岛屿资源、海洋资源、港口航道等优势资源的开发利用提出了科学与合理的建议,以提高舟山市社会、经济和生态三大效益,促进海岛区域的持续发展。     

美术颜料废水治理技术

针对美术颜料生产过程中产生的废水特点，通过实验研究，有针对性地开发出美术颜料废水治理技术，并在示范工程中得到应用，进一步验证了此项技术的可行性。     

Chemical Tracking and Marine Environmental Impact of Ocean Disposal of Calcium Carbonate Residue in the North Yellow Sea

The objective of this study is to determine the sedimentation rate and dispersion area of calcium carbonate residue dumped at sea and the impact to marine environment of dumping by a laboratory simulation experiment; chemical tracking in the field with the help of acoustic and optical tracking; and a comparative study of baseline conditions and marine environmental impact after dumping. Turbidity, pH and phosphate are selected as the chemical tracers to be monitored.

Results show that in the dumping area of 15 square miles with water depth of 50 m, if 217 t calcium carbonate residue is dumped (spot dumping) in the presence of a pycnocline with a current velocity of 60 cm/s (close to the maximum) the maximum dispersion distance of the calcium carbonate residue plume front is less than 2100 m; the dispersion area is less than 0.56 km²; and the maximum dispersion time is about 60 min when the turbidity and pH in the whole dispersion area return to background level. Therefore, the ocean disposal of calcium carbonate residue is feasible.