Feb 2012, Volume 6 Issue 1

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    Yi QIAN
    Bin WANG, Jun HUANG, Shubo DENG, Xiaoling YANG, Gang YU

    The Stockholm Convention on persistent organic pollutants (POPs) was adopted in 2001. This year is the 10th anniversary of the adoption of the Convention. Until now, 22 chemicals or chemical categories have been listed as POPs in the Stockholm Convention. The POPs Research Center was established in Tsinghua University in the same year when the Convention was adopted. In the last ten years, much work has been done by Chinese researchers to understand the environmental risk of POPs in China. This article aims to review the recent research progress of our POPs Research Center and some other Chinese researchers’ studies in addressing the environmental risk of POPs, including the priority screening and inventory study of POPs, monitoring and modeling of POPs pollution and exposure, and environmental risk assessment and modeling of POPs. Although great advances in addressing the environmental risk of POPs have been made in recent years, we are still facing quite a few problems, such as data scarcity and uncertainty in environmental risk assessment of POPs. The study on the effect of POPs mixtures is in its infancy and currently POPs are usually assessed from legal perspective by risk assessment of single chemicals. These problems should be well addressed by further efforts. Further studies should also be taken in future to study environment risk of POPs by considering aspects of coupled dynamics between climate processes and POPs. Such sound scientific, risk-based information can support decision-making aiming to effectively minimize the risk level of POPs.

    Yuchi LEE, Shanglien LO, Jeff KUO, Chinghong HSIEH

    Microwave-hydrothermal treatment of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S2O82-) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects of pH (pH= 2.5, 6.6, 8.8, and 10.5), chloride concentrations (0.01–0.15 mol·L-1), and temperature (60°C, 90°C, and 130°C) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol·L-1 at 90°C and 0.06 mol·L-1 at 60°C, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.

    Osamu SHITAMICHI, Taiki MATSUI, Yamei HUI, Weiwei CHEN, Totaro IMASAKA

    An authentic mixture of polychlorinated biphenyls was measured using a short wide-bore capillary column for the group separation of major components present in an actual sample of Kanechlor. The limits of detection were improved by ca. 2 fold in comparison with those obtained using a conventional capillary column, since the retention time was reduced and the amount of analytes introduced into the mass spectrometer per unit time could be increased. On the other hand, surface-water and sediment samples containing polycyclic aromatic hydrocarbons (PAHs) were collected from the river located in the vicinity of a waste water treatment plant. Even acenaphthylene, a minor component of the mixture could be measured for the sediment sample, and the concentrations were determined for several heavy PAHs. As demonstrated, a technique involving laser multiphoton ionization/time-of-flight mass spectrometry was useful as a sensitive and selective analytical tool for the trace analysis of persistent organic pollutants in an environmental sample.

    Hongliang JIA, Liyan LIU, Yeqing SUN, Daoji CAI, Jianxin HU, Nanqi REN, Yifan LI

    This paper reviews the usage and emissions of endosulfan, the newest member of the persistent organic pollutants (POPs), in China, and its fate and behavior in Chinese environment. Endosulfan usage in China has been estimated to be approximately 25700 t between 1994 and 2004. Concentrations of endosulfan in different environmental compartments in China, such as air, soil, water, and biota, but focusing at air and surface soil, have been summarized. Concentrations of total endosulfan in surface soil across China were ranged from below detection limit (BDL) to 19000 pg·g-1 dry weight (dw), with geometric mean of 120 pg·g-1dw. The results indicated that endosulfan sulfate had highest concentration in Chinese soil, followed by β- and α-endosulfan. Air concentrations of endosulfan in China were ranged 0–340 pg·m-3 for α-endosulfan and 0–121 pg·m-3 for β-endosulfan, with high concentrations occurred in the cotton production areas. Gridded usage inventories of endosulfan on a fine gridded system with a 1/4° longitude by 1/6° latitude resolution were compiled, from which, emission to air and residues in soil of endosulfan were calculated in each grid by using a modified simplified gridded pesticide emission and residue model (SGPERM), an integrated modeling system combining mathematical model, database management system, and geographic information system. Total emissions were around 10800 t from 1994 to 2004. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell, which are in general consistent with the published monitoring data.

    Zhigang LIU, Shaomin ZHU, Yansheng LI

    A novel method for the regeneration of cation exchange resins by aluminum (Al) salts was investigated in order to improve the regeneration efficiency of resins and reduce the dosage of regenerant. The influences of Al3+ concentration and the pH of regeneration solution on resin transformation had been studied. The desalination experiments were carried out to evaluate the characteristics of the Al form resins. Experimental results showed that the regeneration rate of resins was strictly dependent on Al3+ concentration and the pH of the solution. Compared to the conventional regeneration method, the Al form mixed bed exhibited the same desalination capability as the H form mixed bed (MB), and the total organic carbon (TOC) removal was up to 90%, clearly higher than that of the H form. Al salt solution could be utilized repeatedly to regenerate Al form resins.

    Fengyu ZAN, Shouliang HUO, Beidou XI, Xiulan ZHAO

    The biosorption of Cd2+ and Cu2+ onto the immobilized Saccharomyces cerevisiae (S. cerevisiae) was investigated in this study. Adsorption kinetics, isotherms and the effect of pH were studied. The results indicated that the biosorption of Cd2+ and Cu2+ on the immobilized S. cerevisiae was fast at initial stage and then became slow. The maximum biosorption of heavy metal ions on immobilized S. cerevisiae were observed at pH 4 for Cd2+ and Cu2+. by the pseudo-second-order model described the sorption kinetic data well according to the high correlation coefficient (R2) obtained. The biosorption isotherm was fitted well by the Langmuir model, indicating possible mono-layer biosorption of Cd2+ and Cu2+ on the immobilized S. cerevisiae. Moreover, the immobilized S. cerevisiae after the sorption of Cd2+ and Cu2+ could be regenerated and reused.

    Lixia JIN, Mengchang HE, Jinghuan ZHANG

    Sorption isotherms of galaxolide (HHCB) of different fractions from two sediments with different mineral and organic carbon contents were determined to compare HHCB sorption behavior and contribution to the total sorption. The HHCB sorption isotherms that used the batch equilibration method were studied on different sediments of different fractions. The sorption isotherms of 600°C heating fractions were detailed using the linear model, while the other fractions were nonlinear and fitted well with the Freundlich model. The dissolved organic carbon (DOC) removed, NaOH extracted, and 375°C heating fractions showed more nonlinear sorption than the original sediments, which suggested more heterogeneous sorption sites in these fractions. Compared to the original sediments, the 375°C heating fractions had higher carbon-normalized distribution coefficient (Koc) values, indicating a higher sorption affinity for HHCB. Among the different sediment fractions, the contribution of the 600°C heating fractions to the overall sorption were the lowest (<20%), while the 375°C heating fractions were the highest (up to 85%).

    Wenfeng SUN, Ruibao JIA, Baoyu GAO

    In this paper, a method using solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS) was developed to simultaneously analyze five taste and odor compounds in surface water, i.e., 2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (TCA), 2-isopropyl-3-methoxy pyrazine (IPMP), 2-isobutyl-3-methoxy pyrazine (IBMP), and trans-1,10-dimethyl-trans-9-decalol (geosmin, GSM). The mass spectrometry was operated in selective ion monitoring (SIM) mode. Three kinds of SPE columns and three eluting solvents were compared, the C18 column was chosen as optimum SPE column, and methanol was chosen as the optimum eluting solvent. It was found that the method showed good linearity in the range of 1–200 ng·L-1 and gave detection limits of 0.5–1.5 ng·L-1 for individual compounds. Good recoveries (93.5%–108%) and relative standard deviations (1.58%–7.31%) were also obtained. Additionally, concentrations of these taste and odor compounds in Jinan’s surface and drinking water were analyzed by applying this method, and the results showed that GSM and 2-MIB were the dominant taste and odor compounds in Jinan’s raw water.

    Mingsong WU, Junli HUANG, Yuling ZHANG, Shijie YOU, Shaofeng LI, Zhilin RAN, Yu TIAN

    Microcystins, which represents one kind of cancerogenic organic compounds, is abundant in eutrophication water. The effects of reaction factors on chlorine dioxide (ClO2) for removal of low-concentration Microcystin-LR, Microcystin-RR, and Microcystin-YR in water as well as the reaction mechanisms was investigated by using enzyme-linked immunosorbent assay (ELISA) kit and gas chromatography–mass spectrometry (GC-MS). The results showed that MC-LR, MC-RR, and MC-YR could be efficiently decomposed by ClO2. The degradation efficiency was shown positively correlated to the concentration of ClO2 and reaction time; while the effect of reaction temperature and pH is slight. The kinetic constants and activation energies of the reaction of MC-LR, MC-RR, and MC-YR with ClO2 are determined as 459.89, 583.15, 488.43 L·(mol·min)-1 and 64.78, 53.01, 59.15 kJ·mol-1, respectively. As indicated by high performance liquid chromatography mass spectrometer (HPLC-MS) analysis, degradation should be accomplished via destruction of Adda group by oxidation, with the formation of dihydroxy substituendums as end products. This study has provided a fundamental demonstration of ClO2 serving as oxidizing disinfectant to eliminate microcystins from raw water source.

    Dawen GAO, Yu TAO

    Microbes are vital to the earth because of their enormous numbers and instinct function maintaining the natural balance. Since the microbiology was applied in environmental science and engineering more than a century ago, researchers desire for more and more information concerning the microbial spatio-temporal variations in almost every fields from contaminated soil to wastewater treatment plant (WWTP). For the past 30 years, molecular biologic techniques explored for environmental microbial community (EMC) have spanned a broad range of approaches to facilitate the researches with the assistance of computer science: faster, more accurate and more sensitive. In this feature article, we outlined several current and emerging molecular biologic techniques applied in detection of EMC, and presented and assessed in detail the application of three promising tools.

    Bo WEI

    Proteorhodopsin (PR) is a recently discovered protein involved in the utilization of light energy. Several studies have shown that PR-containing microorganisms are widespread and compose a large proportion of the biomass in marine ecosystems. A better understanding of the ecological role of PR will help clarify the effect of the global flow of energy and the carbon cycle on marine communities. In this study, a bioinformatical database of PR codon sequences, the Global Distribution Database of Proteorhodopsin (GDDP), as a tool for analyzing the diversity and distribution of PR-containing microorganisms in marine environments throughout the world was designed. The community structure of PR microorganisms were also compared using PCR assays and UniFrac analyses of 12 samples collected from three water layers (0, 75, and 200 m) at four representative sites in the Pacific, Atlantic, and Indian Oceans. The results indicate that PR-containing microorganisms can be grouped into two distribution types: widespread and location-specific. Representative cases of the former include SAR11-PR and HOT2C01-PR. Interestingly, PR communities cluster by geographic locale but not by water depth.

    Hongwei QIN, Liufang CHEN, Nan LU, Yahui ZHAO, Xing YUAN

    In this article, the toxic effects of Enrofloxacin (ENFX) on Scenedesmus obliquus were studied, through investigating the growth, photosynthetic pigments, and protein contents. The possible toxic mechanisms of ENFX were analyzed by determining the superoxide dismutase (SOD) activity, malondialdehyde (MDA) content, proline content, and superoxide anion (O2-) generation rate. Results showed that the growth of algae was inhibited by ENFX and the 50% effective concentration (EC50) values for 24, 48, 72, and 96 h of ENFX were 88.39, 63.86, 45.10, and 59.16 mg·L-1, respectively. After treated with ENFX for 96 h, the contents of photosynthetic pigments decreased with the increase of ENFX concentration, the content of soluble protein and the activity of SOD increased and then decreased, and the generation rate of superoxide anion (O2-) increased continually. The contents of MDA and proline changed little in lower ENFX concentration groups, but increased rapidly when treated with higher concentration groups. These results suggested that ENFX affected the growth of S. obliquus, and the main toxicity mechanism was that algal cells generated the reactive oxygen species under ENFX stress, and then the reactive oxygen species (ROS) induced the oxidation damages of biologic macromolecules and changed the biomembrane permeability further.

    Min YUE, Qinyan YUE, Yuanfeng QI, Baoyu GAO, Hui YU

    In this work we investigated the chemical, thermal and toxic properties of dried sewage sludge (DSS), the preparation and properties of lightweight sludge ceramic (LSC) and the mechanisms of action of the organic and inorganic foaming agents (OFAs and IFAs). The chemical components and thermal properties of the raw materials were studied by Energy Dispersive X-ray Detection (EDX) and Thermogravimetric Analysis and Differential Scanning Calorimetry (DSC/TGA). The mineral phases of the raw materials and the formed ceramics were determined by X-ray Diffraction (XRD). The leaching characteristics of heavy metals were investigated with Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). Different ratios of DSS and clay were mixed and pressed into raw pellets. After drying and preheating treatment, the raw pellets were sintered at 1150°C for 10 min. The physical properties of LSC (50 wt% DSS added) were tested. The results showed that when the addition of DSS was above 50 wt%, LSC began to shrink, and a maximum density occurred. The environmental safety of LSC was satisfactory. XRD showed that some new mineral phases formed in the LSC. Observation of the microstructure by Scanning Electron Microscope (SEM) indicated that the body of LSC was porous.

    Guochen ZHENG, Jianzheng LI, Feng ZHAO, Liguo ZHANG, Li WEI, Qiaoying BAN, Yongsheng ZHAO

    To investigate the influence of illumination on the fermentative hydrogen production system, the hydrogen production efficiencies of two kinds of anaerobic activated sludge (floc and granule) from an anaerobic baffled reactor were detected under visible light, dark and light-dark, respectively. The 10 mL floc sludge or granular sludge was respectively inoculated to 100 mL diluted molasses (chemical oxygen demand of 8000 mg·L-1) in a 250 mL serum bottle, and cultured for 24 h at 37°C under different illumination conditions. The results showed that the floc was more sensitive to illumination than the granule. A hydrogen yield of 19.8 mL was obtained in the dark with a specific hydrogen production rate of 3.52 mol·kg-1MLVSS·d-1 (floc), which was the highest among the three illumination conditions. Under dark condition, the hydrogen yield of floc sludge reached the highest with the specific hydrogen production rate of 3.52 mol·kg-1MLVSS·d-1, and under light-dark, light, the specific hydrogen production rate was 3.11 and 2.21 mol·kg-1MLVSS·d-1, respectively. The results demonstrated that the illumination may affect the dehydrogenase activity of sludge as well as the activity of hydrogen-producing acetogens and then impact hydrogen production capacity.

    Ling-Ling Wang, Shan Chen, Hai-Ting Zheng, Guo-Qing Sheng, Zhi-Jun Wang, Wen-Wei Li, Han-Qing Yu

    Since the living microorganisms in activated sludge continuously change, it is difficult to conduct controlled experiments and achieve reproducible results for evaluating sludge characteristics. Synthetic sludge, as a chemical surrogate to activated sludge, could be used to investigate the sludge physicochemical properties, and it is desirable to prepare synthetic sludge with similar structure and properties to real activated sludge to explore the flocculation and settlement processes in activated sludge systems. In this work, a high-strength synthetic sludge was prepared with functional polystyrene latex particles as the framework and extracellular polymeric substances (EPS) to modify its surface. The flocculation and settling characteristics of the microspheres and the prepared synthetic sludge were tested. Compared with other three functional polystyrene latex microspheres, the synthetic sludge prepared with EPS-modified polystyrene latex microspheres showed good settling characteristics and a significantly higher strength. They could be used for studying the physicochemical properties of activated sludge.

    Yue WEN, Chao XU, Gang LIU, Yi CHEN, Qi ZHOU

    The purpose of this study is to reduce the seasonal fluctuation and enhance the efficiency of nitrogen removal in vertical flow-horizontal subsurface flow (VF-HSF) constructed wetlands. Two sets of VF-HSF constructed wetlands were built, VF1-HSF1 and VF2-HSF2, and a zeolite section was placed in VF2. The results showed that VF2-HSF2 compared to VF1-HSF1 was not only a more reliable nitrogen removal method, but also enhanced the nitrogen removal efficiency by 50%. The average apparent rate of nitrogen removal in VF2-HSF2 reached to 2.52 gN·m-3·d-1, which doubled the rate in VF1-HSF1. Plant uptake and organic nitrogen sediment accounted for 12% and 6% of the total nitrogen removal in VF1-HSF1, respectively, and 10% and 4% in VF2-HSF2, respectively. Biologic nitrogen removal was the dominant mechanism, which accounted for 79% and 87% of the total nitrogen removal in VF1-HSF1 and VF2-HSF2, respectively. Ammonia adsorbed by zeolite during the cold seasons was desorbed, and then nitrified in warm seasons, which resulted in a bioregeneration efficiency of 91%. Zeolite in VF was capable of transferring ammonia from cold seasons to warm seasons as well as enhancing nitrification, which was accompanied by high potential denitrification in HSF that reinforced the efficiency and relieved seasonal fluctuation of nitrogen removal in VF-HSF.