Table of Content

30 April 2016, Volume 22 Issue 2

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Concentration levels and distribution features of PAEs in water environment in Shanghai

WU Minghong, WANG Fulin, YANG Xuexia, SHI Mingge, XU Gang

2016, 22(2):  105-113.  doi:10.3969/j.issn.1007-2861.2016.02.004

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Having selected 5 waste water treatment plants and 11 sampling points in Huangpu River, Shanghai, as research objects, a solid phase micro-extraction (SPME) mode was took to measure phthalate esters (PAEs) in waters. The results showed that diisobutyl phthalate (DIBP), benzyl butyl phthalate (BBP) and di(2-ethylhexyl) phthalate (DEHP) were major contributors of PAEs concentration, thus making them the main pollutants in Huangpu River. DIBP claimed much more responsibility than any other PAEs for the PAEs concentrations during inflow in waste water treatment plants. The PAEs concentrations decreased tremendously during outflow, and were far lower than those during inflow. With the average removal rate in 5 sewage water plants exceeding 70%, PAEs had been very well disposed. Ranging from 18.071~346.662 μg/L, PAEs concentrations in surface water were much lower in agricultural watersheds in the upstream than in business areas in the downstream of Huangpu River. A correlation analysis between PAEs discharged by water treatment plants and PAEs in Huangpu River showed no direct relevance between them. Therefore, specific sources of water pollutants in surface water requires further research.

Research progress of environmental persistent free radicals

RUAN Xiuxiu, SUN Wanxue, CHENG Ling, QIAN Guangren

2016, 22(2):  114-121.  doi:10.3969/j.issn.1007-2861.2016.01.002

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Environmental persistent free radicals (EPFRs) is a new kind of environmental risk product, which may exist permanently in the environment with paramagnetic stability. This paper introduces the features, formation mechanism and influence factors of EPFRs. It is summarized that EPFRs has stronger environmental sustain ability and toxicity. Potential applications of EPFRs are introduced such as degrading organic matter by EPFRs to activate certain compounds and produce reactive oxygen species.

Spatial and temporal variations of organochlorine pesticides in surface water, sediments and fishes collected from Dianshan Lake and the#br# associated human health risk

ZHANG Xiaolan, GU Yue, LI Xiaojing, YU Yingxin

2016, 22(2):  122-130.  doi:10.3969/j.issn.1007-2861.2016.01.005

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Organochlorine pesticides (OCPs) are persistent organic pollutants. It can provide fundamental data to help researchers comprehensively understand the influence of contaminants inalake aquatic environment, investigate contamination levels and distribution characteristics of OCPs. The results showed that hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and its metabolites were the main OCPs in surface water and sediments, respectively. Accumulation of OCPs in wild fishes was observed.DDTs and HCHs in the lake were mainly historical residues. OCPs’ concentrations in
sediments were stable, while those in surface water varied during the sampling period. Concentrations of contaminants in surface water were higher in wet season than in dry season. The contaminant levels in the inlet area were higher than in the effluent area. Dietary intake of fishes and water was the main exposure sources of DDTs and HCHs, but the contamination level was low, and it did not lead to significant health risks.

 

Seasonal and spatial distributions of chlorinated PAHs in road dust from downtown Shanghai

WU Minghong1, WANG Yujie1, LIU Wenlong1, TANG Liang1, KANNAN Kurunthachalam2, OHURA Takeshi3, MA Jing1

2016, 22(2):  131-140.  doi:10.3969/j.issn.1007-2861.2016.01.001

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Concentrations of twenty chlorinated polycyclic aromatic hydrocarbons (ClPAHs) in road dust from downtown Shanghai were analyzed using gas chromatographymass spectrometry (GC/MS). Eleven of twenty ClPAH congeners were found in road dust samples with more than a detection rate of 50%, indicating that ClPAHs were ubiquitous in road dust in downtown Shanghai. Seasonal variability of ClPAHs concentrations were observed, with higher concentrations in winter than in summer. The highest concentration of total ClPAHs was 24.9 ng/(g dw) (dw means dry weight) in winter. Concentrations of
ClPAHs varied greatly in different functional areas, In particular, the highest concentration was found in transportation hub regions (21.2 ng/(g dw) in winter and 10.7 ng/(g dw) in summer) followed by construction and commercial areas, while the lowest concentration was found in green areas. The compositional analysis showed that 6-ClBaP and 7-ClBaA were the two most important components in the road dust samples. The toxic equivalent
quantity (TEQ) ranges of ClPAHs were 0.01~4.81 ng-TEQ/(g dw) in winter and 0.01~1.78 ng-TEQ/(g dw) in summer, and the toxic equivalent of 7-ClBaA contributed the most.

Levels of polybrominated diphenyl ethers in surface soil of Guiyu and the associated health risk to children

LOU Sufang1, WANG Xinxin1, JIANG Zi’an1, LU Shaoyou2, YU Yingxin1

2016, 22(2):  141-150.  doi:10.3969/j.issn.1007-2861.2016.01.007

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A total of 12 surface soil samples were collected from Guiyu of Guangdong Province, and the concentrations of polybrominated diphenyl ethers (PBDEs) including 14 congeners were determined. The results showed that the area was contaminated by PBDEs. The total concentrations of PBDEs ranged from 76.5 to 13 354.0 ng/(g dw) (dw meas dry weight), which were much higher than other regions. Among the 14 congeners, BDE209 was the prominent congener, followed by BDE47, BDE99, and BDE183, which indicated that technical Deca-BDE product was the main source of the PBDEs in the sampling sites, and technical Penta- and Oct-BDEs were also the important contributors. The estimated daily intakes and uptakes of PBDEs via oral ingestion and dermal contact by children were calculated, and the associated health risks at non-carcinogenic endpoint were assessed by using hazard quotient (HQ). The results showed that the estimated daily intakes of PBDEs vary from 31.1 to 5 430.0 and from 7.7 to 1 335.0 ng/d, respectively, and the dermal contact was the main pathway. Whereas, when the uptake efficiency of PBDEs was added into the calculation, the estimated daily uptakes of PBDEs decreased to 0.3～54.3 and 1.3～184.0 ng/d, respectively, and the oral ingestion was the main pathway then. In both cases, the HQ values were much less than 1, indicating that PBDEs in the area would not lead significant health risk to the local children.

Investigation of heavy metal pollution in soil around chemical industrial area in Shanghai

LI Yinyin1,2, HE Chiquan1

2016, 22(2):  151-158.  doi:10.3969/j.issn.1007-2861.2016.01.020

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The pollution status and potential ecological risks of heavy metal in soil around chemical industrial area in Shanghai were studied. Spatial variation structures of 13 heavy metals (Ag, As, Be, Cd, Cr, Cu, Ni, Pb, Se, Sb, Tl, Zn and Hg) in the soil were analyzed. Single and composite pollution indices were used to evaluate heavy metal pollution in soil. The results showed that average concentrations of Ag, As, Be, Cd, Cr, Cu, Ni, Pb, Se, Sb, Tl, Zn and Hg were 0.10, 10.20, 2.50, 0.60, 93.00, 78.00, 33.80, 14.90, 1.00, 3.45, 0.40, 124.00, 0.19 mg/kg, respectively. According to the Grade A Standard of Soil Quality Assessment for Exhibition Sites, the over-limit rates of Cu, Zn and Cd were 12.20%, 8.16%, and 8.16%, respectively. The over-limit rates of Cr, Ni, Sb and Hg were between 4.08% and 6.12%. Pollution in the surface and medium-layer soil in this area was more serious. The heavy metals’ concentration decreased with the increase of sampling depth at some monitored sites. With the study of correlation between soil heavy metal elements, it showed that the homology of heavy metal pollution and combined pollution in the soil.

Dicarbonyl compounds and formation secondary organic aerosol in atmosphere

ZHOU Huan, FENG Yanli, JIANG Zhiming, QIU Yiqin, ZHANG Wensheng

2016, 22(2):  159-171.  doi:10.3969/j.issn.1007-2861.2016.01.012

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Contribution of secondary organic aerosol (SOA) to atmospheric haze is a hot topic in atmospheric chemistry. Dicarbonyl compounds (glyoxal and methylglyoxal) are intermediate products in atmospheric photochemical reactions, greatly contributing to the formation and growth of SOA. Dicarbonyl compounds in the atmosphere mainly come from biogenic sources such as isoprene and anthropogenic source such as acetylene and other volatile organic compounds oxidation. Dicarbonyl compounds can form SOA by gas particle partitioning, which is a reversible process. Dicarbonyl compounds can produce significant aerosol yields, attributed to hydration, polymerization and oxidation and other reactions to produce low volatile products, which is an irreversible process. A common detection method of dicarbonyl compounds is to use gas chromatography-mass spectrometry (GC/MS) after derivatization.

Composition of secondary organic aerosol and its contributions to organic carbon in PM_2.5

JU Fashuai, WANG Xintong, HAN Dewen, WANG Wu

2016, 22(2):  172-180.  doi:10.3969/j.issn.1007-2861.2016.01.021

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PM_2.5 samples collected during summer were analyzed with gas chromatographymass spectrometry (GC/MS). The purposes were to study the concentration levels and influence factors of secondary organic aerosol (SOA) formation, and estimate the contributions of secondary organic carbon (SOC) to organic carbon (OC) using a tracer-yield method. Isoprene tracers had a large percentage of total SOA tracers, which were 31.3% to 52.2%. The dominant isoprene tracer was 2-methylglyceric acid. -pinene SOA tracers had a small percentage of total SOA tracers, which were 16.4% to 35.8%. Concentration
of toluene tracers ranged from 6.49 to 12.60 ng/m³, higher than Baoshan, Shanghai and Hong Kong, China, and lower than Beijing and Guangzhou. The contributions of SOC of toluene to OC were 11.5%～17.7% and SOC of toluene were important parts of SOC, indicating that anthropogenic emissions were important sources of air pollution. Positive correlation existed between SOA tracers and O₃, indicating that O₃ had great influence on
SOC formation.

Combined effects of 1-nitropyrene and benzo(a)pyrene on cytotoxicity and DNA damage in human lung epithelial A549 cells

SHANG Yu, ZHOU Qian, JIANG Yuting

2016, 22(2):  181-187.  doi:10.3969/j.issn.1007-2861.2016.01.008

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Using human lung epithelial A549 cells, combined toxic effects of 1-nitropyrene (1-NP) and benzo(a)pyrene (B[a]p) were evaluated. The 1-NP caused a significantly concentration-dependent viability decrease, DNA damage and reactive oxygen species (ROS) generation. Compared with the groups treated with 1-NP alone, viability was significantly increased and ROS generation was significantly reduced in combined-treated groups with 1-NP and B[a]p. However, the DNA damage was significantly increased in the combinedtreated groups compared with the groups treated with 1-NP alone. These results suggested that 1-NP may mediate the cytotoxic effects through ROS generation, and pretreatment, with B[a]p may inhibit ROS generation induced by 1-NP, and thereby reducing the cell death in A549 cells. However mechanisms of DNA damage deserves further investigations.

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HU Xing, DU Liting, WANG Fei, BAI Xiaoqing, LIU Xuelan, YANG Yang

2016, 22(2):  188-196.  doi:10.3969/j.issn.1007-2861.2016.01.003

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Effects and improvement suggestions of green account system for waste classification and reduction in Shanghai

WU Jianzhong, ZHOU Xujie, YAN Xiaofang, WANG Fei, BAI Xiaoqing, LI Yongping, WANG Yuhua, ZHOU Jizhi

2016, 22(2):  197-202.  doi:10.3969/j.issn.1007-2861.2016.01.009

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Establishment of a green account system is a major strategy to promote waste classification and reduction in Shanghai. A green account system was evaluated in terms of efficiency by visiting residents and surveying the literature. The results revealed that the two challenges to the current system were the large budget and low enthusiasm of the residents in garbage sorting. Two innovations were proposed to improve the system. One was to adjust payment of subsidy to the classification assistant to enhance relevance between the green account and waste classification. Another was to construct a platform to promote the green account, in which a sustainable driving force was built to link the residents’ classification behavior and their consuming. All these can make a breakthrough in popularizing the green account and promote waste classification.

Removal of Cr(Ⅵ) in soil by chitosan stabilized nanoscale zero iron

YAN Lijun1,2, LIU Moli1, HU Xuefeng1

2016, 22(2):  203-210.  doi:10.3969/j.issn.1007-2861.2016.01.011

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Removal efficiency of Cr(Ⅵ) in soils by chitosan stabilized nanoscale zero-valent iron was studied. Experimental results showed that the removal efficiency increased with zero-valent iron dosage. The maximum removal efficiency was 95.9%, six times of 100 mesh iron filing. The initial concentration of Cr(Ⅵ) in soil and pH value were all inversely proportional to the removal efficiency. Removal of Cr(Ⅵ) in soils by zero-valent iron was a result of the interaction of adsorption and reduction. The reduction process of nanoscale zero-valent iron accorded with pseudo first-order reaction kinetics, and the apparent rate constant kobs was 0.016/min.

Anti-scale performance of polyepoxysuccinic acid with conductivity measurement

ZHU Shuiping, CAO Liya, YIN Tiantian, WANG Chaoqun, LIU Xiaoyan

2016, 22(2):  211-217.  doi:10.3969/j.issn.1007-2861.2016.01.006

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With the proposal and development of green chemistry, corrosion inhibitors tend to be environmental friendly. This paper explores the anti-scale performance of polyepoxysuccinic acid (PESA) on CaCO₃ scale, BaCO₃ scale, BaSO₄ scale at different temperatures and different concentrations with conductivity measurement. The results showed that the ability of anti-scale performance of PESA was good. With the increasing of its concentration, the anti-scale performances of PESA on CaCO₃ and BaSO₄ continued to strengthen, while BaCO₃ decreased after the concentration rised to 40 mg/L. With temperature
increasing, its anti-scale performance of CaCO₃ scale decreased, while BaCO₃ scale and BaSO₄ scale increased. Therefore, PESA is an excellent anti-scale inhibitor suitable for inhibiting CaCO₃, CaSO₄, and BaSO₄ at normal temperature of the factory. Moreover, the conductivity measurement is simple and fast, and it can be used in exploring the anti-scale performance of scale inhibitors.

Preparation of layered Cu/ZnO/Al₂O₃ catalyst and its catalytic performance for CO₂ hydrogenation to methanol

XIAO Shuo1,2, GAO Peng2, YANG Haiyan2, XIA Lin2, ZHANG Jianming2, CHEN Zhiwen1, WANG Hui2

2016, 22(2):  218-230.  doi:10.3969/j.issn.1007-2861.2015.05.019

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Layered Cu/ZnO/Al₂O₃ catalysts were prepared with ahomogeneous precipitation method using urea hydrolysis. The mixed oxides were then obtained by the calcination and reduction of precursors and tested for methanol synthesis from CO₂ hydrogenation. The prepared materials were characterized by X-ray diffraction (XRD), thermogravimetric(TG), scanning electron microscope (SEM), X-ray fluorescence (XRF), BET, H₂-temperature program reduction (H₂-TPR), N₂O chemisorption, and CO₂-temperature program desorption (CO₂-TPD) techniques. Compared with the catalysts prepared by conventional co-precipitation method, the crystallinity degree of precursors, the BET specific surface area and dispersion of copper were increased with ahomogeneous precipitation method. This improvement was significant with reflux treatment during the homogeneous precipitation process. Evaluation of these catalysts for CO₂ hydrogenation to methanol revealed that the CO₂ conversion increased with increase of Cu specific surface area, and methanol selectivity was related to the proportion of strongly basic sites. Therefore, the maximum methanol yield was obtained over the Cu/ZnO/Al₂O₃ catalyst prepared using ahomogeneous precipitation method with reflux treatment.

Influence of charge collection efficiency on energy spectrum for planar CdZnTe detector

LI Yang1, LUO Wenyun1, JIA Xiaobin1, ZHANG Jialei1, WANG Linjun2

2016, 22(2):  231-237.  doi:10.3969/j.issn.1007-2861.2016.01.004

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Using Monte-Carlo code Geant4 to model the planar CdZnTe detector, the incidences of two different energy ray ²⁴¹Am (59.5 keV) and ¹³⁷Cs (662 keV) to the planar CdZnTe detector from the cathode surface perpendicularly were simulated. The charge collection efficiency was calculated by adding the Hecht equation in Geant4. Combined with distributions of the deposited energy, electron-hole pairs and the interaction types, the influence of charge collection efficiency on the energy spectrum was discussed. The results showed that the energy spectrum shifted to the low energy side after considering the charge collection efficiency. The shift was closely connected to the maximum charge collection efficiency.

Preparation and properties of Ni-doped SnO₂ nanospheres for lithium-ion battery anode materials

MIAO Chunjie, HU Zhixiang, REN Lanlan, GAO Ziming, DONG Jingyu, LI Qi, LUO Zhigang, CHEN Zhiwen

2016, 22(2):  239-244.  doi:10.3969/j.issn.1007-2861.2015.05.020

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Ni-doped SnO₂ nanospheres were synthesized with a facile one-step hydrothermal method as a high-performance anode material for lithium-ion batteries. Scanning electron microscope (SEM), high resolution transmission electron microscope (HRTEM), Raman analyzer, X-ray diffraction (XRD) and electrochemical performance testing equipment such as blue electrical test systems and electrochemical workstation were used to investigate morphology, composition, crystallization behavior and electrochemical properties of Ni-doped SnO₂ and find the best doping reaction time. It has been found that the appropriate Ni-doped SnO₂ nanospheres showed much better rate capability and excellent cycling performance compared with the pristine SnO₂. In particular, the sample of 5%  Ni-doped SnO₂ whose reaction time was 12 h showed a high initial discharge capacity of 1 970.3 mA·h/g at a current density of 100 mA/g, far higher than the theoretical capacity of SnO2 of 782 mA·h/g. This was because Ni-doping could accommodate huge volume expansion and avoid agglomeration of nanoparticles. Thus, the electrochemical performance of Ni-doped SnO₂ nanospheres was significantly improved.

Characteristics and pore structures of shale reservoir rocks in eastern and southeastern Chongqing of China

ZHU Yangsheng1,2, SONG Xuehang2, GUO Yintong3, XU Feng3, SUN Nannan2, WEI Wei2,4, CHEN Zhiwen1

2016, 22(2):  246-260.  doi:10.3969/j.issn.1007-2861.2015.05.021

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Elemental compositions, mineral compositions, reservoir space types and mechanical properties of shale samples from the Lower Silurian Longmaxi Formation and Lower Jurassic Ziliujing Formation were investigated by X-ray diffraction (XRD), gas adsorption (N₂, CO₂) analysis, field emission-scanning electron microscope (FE-SEM), X-ray photoelectron spectroscopy (XPS), and uniaxial compressive tests. It was found that both formations arecharacterized by relatively high brittleness, high elastic modulus and lowPoisson’s ratio. That was advantageous for fracturing. To be more specific, each sample
was composed of quartz, clay, feldspar, calcite, dolomite, pyrite, berlinite and other minerals. In general, quartz content was higher than 45%, while clay content was relatively low(24.4%~32.5%), with chlorite, illite and kaolinite representing the major components. The SEM results indicated that pores could be classified into four types, namely intragranular pore, intergranular pore, organic matter pore and microfracture. In addition, the porosity of sample was 5% (capacity) with diameters mainly in the range of 0~20 nm.The BET specific surface areas and pore volumes were positively related to the total organic
carbon content (TOC) and clay content, while brittle minerals had a negative effect to these parameters.