Removal of polycyclic aromatic hydrocarbons from aqueous solution by raw and modified plant residue materials as biosorbents

Removal of polycyclic aromatic hydrocarbons （PAHs）, e.g., naphthalene, acenaphthene, phenanthrene and pyrene, from aqueous solution by raw and modified plant residues was investigated to develop low cost biosorbents for organic pollutant abatement. Bamboo wood, pine wood, pine needles and pine bark were selected as plant residues, and acid hydrolysis was used as an easily modification method. The raw and modified biosorbents were characterized by elemental analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. The sorption isotherms of PAHs to raw biosorbents were apparently linear, and were dominated by a partitioning process. In comparison, the isotherms of the hydrolyzed biosorbents displayed nonlinearity, which was controlled by partitioning and the specific interaction mechanism. The sorpfion kinetic curves of PAHs to the raw and modified plant residues fit well with the pseudo second-order kinetics model. The sorption rates were faster for the raw biosorbents than the corresponding hydrolyzed biosorbents, which was attributed to the latter having more condensed domains （i.e., exposed aromatic core）. By the consumption of the amorphous cellulose component under acid hydrolysis, the sorption capability of the hydrolyzed biosorbents was notably enhanced, i.e., 6-18 fold for phenanthrene, 6-8 fold for naphthalene and pyrene and 5-8 fold for acenaphthene. The sorpfion coefficients （Kd） were negatively correlated with the polarity index [（O＋N）/C], and positively correlated with the aromaticity of the biosorbents. For a given biosorbent, a positive linear correlation between logKoc and logKow for different PAHs was observed. Interestingly, the linear plots of logKoc-logKow were parallel for different biosorbents. These observations suggest that the raw and modified plant residues have great potential as biosorbents to remove PAHs from wastewater.     

Molecular characterization and developmental expression patterns of thyroid hormone receptors (TRs) and their responsiveness to TR agonist and antagonist in Rana nigromaculata

Considering some advantages of Rana nigromaculata as an experimental species, we propose that this species, like Xenopus laevis, could be used to assay thyroid hormone（TH） signaling disrupting actions. To validate the utilizability of R. nigromaculata, we investigated the responsiveness of R. nigromaculata to a TH receptor（TR） agonist（T3） and antagonist（amiodarone） by analyzing expression, based on characterizing TR cDNA and developmental expression patterns. With high levels of identity with the corresponding genes in X. laevis, both TRα and TRβ in R. nigromaculata exhibited roughly similar developmental expression patterns to those of X. laevis, in spite of some species-specific differences. Both TRα and TRβ expression had greater changes in the liver and intestine than in the tail and brain during metamorphosis. T3 exposure for 2 days induced more dramatic increases of TRβ expression in stage 27 than in stage34 tadpoles but not in stage 42 tadpoles, showing that the responsiveness of R. nigromaculata to TH decreased with development and disappeared at the onset of metamorphic climax.Corresponding to greater changes of TRβ expression in the liver and intestine than in the tail and brain during metamorphosis, the liver and intestine had higher responsiveness to exogenous T3 than the tail and brain. Amiodarone inhibited T3-induced TRβ expression. Our results show that R. nigromaculata can be used as a model species for assaying TH signaling disrupting actions by analyzing TRβ expression, and intestine tissues at stage 27 are ideal test materials due to high responsiveness and easy accessibility.     

Inhibitory effects of nisin-coated multi-walled carbon nanotube sheet on biofilm formation from Bacillus anthracis spores

Multi-walled carbon nanotube（MWCNT） sheet was fabricated from a drawable MWCNT forest and then deposited on poly（methyl methacrylate） film. The film was further coated with a natural antimicrobial peptide nisin. We studied the effects of nisin coating on the attachment of Bacillus anthracis spores, the germination of attached spores, and the subsequent biofilm formation from attached spores. It was found that the strong adsorptivity and the super hydrophobicity of MWCNTs provided an ideal platform for nisin coating. Nisin coating on MWCNT sheets decreased surface hydrophobicity, reduced spore attachment, and reduced the germination of attached spores by 3.5 fold, and further inhibited the subsequent biofilm formation by 94.6% compared to that on uncoated MWCNT sheet. Nisin also changed the morphology of vegetative cells in the formed biofilm.The results of this study demonstrated that the anti-adhesion and antimicrobial effect of nisin in combination with the physical properties of carbon nanotubes had the potential in producing effective anti-biofilm formation surfaces.     

Beyond hypoxia：Occurrence and characteristics of black blooms due to the decomposition of the submerged plant Potamogeton crispus in a shallow lake

Organic matter-induced black blooms(hypoxia and an offensive odor) are a serious ecosystem disasters that have occurred in some large eutrophic shallow lakes in China. In this study, we investigated two separate black blooms that were induced by Potamogeton crispus in Lake Taihu, China. The main physical and chemical characteristics, including color- and odor-related substances, of the black blooms were analyzed. The black blooms were characterized by low dissolved oxygen concentration(close to 0 mg/L), low oxidation-reduction potential, and relatively low pH of overlying water. Notably higher Fe2+and∑S2-were found in the black-bloom waters than in waters not affected by black blooms. The black color of the water may be attributable to the high concentration of these elements, as black FeS was considered to be the main substance causing the black color of blooms in freshwater lakes. Volatile organic sulfur compounds, including dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, were very abundant in the black-bloom waters. The massive anoxic degradation of dead Potamogeton crispus plants released dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, which were the main odor-causing compounds in the black blooms. The black blooms also induced an increase in ammonium nitrogen and soluble reactive phosphorus levels in the overlying waters. This extreme phenomenon not only heavily influenced the original lake ecosystem but also greatly changed the cycling of Fe, S, and nutrients in the water column.     

Unregulated emissions from diesel engine with particulate filter using Fe-based fuel borne catalyst

The alteration and formation of toxic compounds and potential changes in the toxicity of emissions when using after-treatment technologies have gained wide attention. Volatile organic compound（VOC）, carbonyl compound and particle-phase polycyclic aromatic hydrocarbon（PAH） emissions were tested at European Steady State Cycle（ESC） to study unregulated emissions from a diesel engine with a fuel-borne catalyst and diesel particulate filter（FBC–DPF）. An Fe-based fuel-borne catalyst was used for this study. According to the results, brake specific emissions of total VOCs without and with DPF were 4.7 and4.9 mg/kWh, respectively, showing a 4.3% increase. Benzene and n-undecane emissions increased and toluene emission decreased, while other individual VOC emissions basically had no change. When retrofitted with the FBC–DPF, total carbonyl compound emission decreased 15.7%, from 25.8 to 21.8 mg/kWh. The two highest carbonyls, formaldehyde and acetaldehyde, were reduced from 20.0 and 3.7 to 16.5 and 3.3 mg/kWh respectively. The specific reactivity（SR） with DPF was reduced from 6.68 to 6.64 mg/kWh. Total particle-phase PAH emissions decreased 66.4% with DPF compared to that without DPF. However, the Benzo[a]pyrene equivalent（BaPeq） with DPF had increased from 0.016 to 0.030 mg/kWh.Fluoranthene and Pyrene had the greatest decrease, 91.1% and 88.4% respectively. The increase of two- and three-ring PAHs with DPF indicates that the fuel-borne catalyst caused some gas-phase PAHs to adsorb on particles. The results of this study expand the knowledge of the effects of using a particulate filter and a Fe-based fuel-borne catalyst on diesel engine unregulated emissions.     

土壤剖面部分多环芳烃源识别参数的纵向变化及成因

通过对北京和天津地区18条土壤剖面样品中PAHs的分析检测及PAHs的土柱淋滤实验模拟研究,得出了部分反映PAHs污染源的分子标志物参数在土壤剖面(或淋滤土柱)上的纵向变化特征,分析了PAHs化合物的纵向迁移作用对这些参数的影响,讨论了部分用于识别土壤中PAHs污染源的分子标志物参数的有效性。结果表明:在土壤剖面0~50 cm范围内,An/Ph,MPI1,MP/P值均有随深度增加而逐渐降低的趋势,在深层(>50 cm)不同剖面之间这些参数值差别不大;Fl/Py随深度增大呈现一定的波动性,但总体波动范围较小,且在0~40 cm变化不大;C0/(C0+C1)P/A和C0/(C0+C1)F/P值变化较为复杂。土柱淋滤实验表明,在0~50 cm范围内,部分PAHs污染源识别参数(An/178、MPI1、MP/P、C0/(C0+C1)F/P和C0/(C0+C1)P/A等)随深度的变化趋势与自然土壤剖面中的变化趋势基本一致,在深层50~100 cm范围内,这些参数值的大小逐渐与原土中的接近。表明淋滤作用(迁移过程)对表层土及土壤剖面浅部(50 cm范围内)部分PAHs污染源参数值的大小有不同程度的影响,运用PAHs污染源识别参数时,这些参数的有效性应引起足够的注意;而剖面深部(>50 cm)PAHs参数值受表层污染物组成的影响较小,其大小主要反映原土中化合物组成及成因。不同剖面受淋滤作用影响的范围存在一定的差别,这主要取决于土壤中TOC的分布特征。     

多层含水层地下水数值模型参数灵敏度分析

为分析多含水层结构地下水数值模型中水文地质参数的影响特征,文章以辽宁阜新某项目区为例,采用地下水模拟软件(GMS)建立具有4层含水层结构的地下水数值模型,并进行拟合校正,选取渗透系数、给水度进行局部灵敏度和全局灵敏度分析。结果表明:渗透系数对模型结果的影响比给水度大;参数变幅为10%时,渗透系数灵敏度是给水度灵敏度的10倍左右;就全局灵敏度而言,参数联合灵敏度大于单个灵敏度之和。     

集合经验模态分解在长江中下游梅雨变化多尺度分析中的应用

基于长江中下游流域5个梅雨监测站1961~2012年的日数据,利用集合经验模态分解（EEMD）方法,对研究期内梅雨时间序列进行多尺度的分析,探讨其在不同时间尺度上的振荡模态结构特征。结果表明：近50多年来,长江中下游梅雨变化呈现出显著的年际和年代际尺度振荡特征,在年际尺度上表现出准3 a和6 a的周期变化,而在年代际尺度上显示准13 a和24 a的周期变化;各分量方差〖JP2〗贡献率显示,年际振荡在梅雨长期变化中占据主导地位;自1961年以来,EEMD分解的梅雨长期变化趋势表现出先增加后减少的倒“U”型特征,其中1961~1985年呈上升趋势,1985~2012年呈下降趋势,尤其是在2000年之后的下降趋势最为明显。由此可以看出,EEMD能够有效地揭示梅雨长期序列在不同时间尺度上的变化规律,可用于诊断非线性、非平稳性信号变化的复杂性特征     

杭州市办公场所室内空气中PBDEs的污染现状与特征

分析评价了杭州市办公场所中PBDEs的污染现状、污染特征.结果表明,办公场所中PBDEs气相和颗粒相总浓度范围为40.66~141.00 pg·m-3,平均浓度为93.22 pg·m-3,是家庭室内、室外浓度的1.87、5.01倍.BDE-47、BDE-99为办公场所中最重要的两种同系物,分别占总浓度的33.29%、31.99%.PBDEs气相浓度是颗粒相的1.34倍,其中BDE-28、BDE-47、BDE-99主要存在于气相中,BDE-153、BDE-183主要存在于颗粒相中.     

TiO2/粉煤灰光催化降解双氯芬酸钠研究

以燃煤电厂外排的废弃物粉煤灰(CFA)为载体,采用混合泥浆法将TiO2负载在CFA的表面,得到一种新型的复合光催化剂TiO2/CFA.对TiO2/CFA进行了扫描电镜分析、X射线衍射分析和氮吸附测试,并以双氯芬酸钠的光催化降解为评价手段,研究了TiO2负载量对TiO2/CFA光催化性能及重复使用性能的影响.结果表明,TiO2负载量的增加有助于提高TiO2/CFA的光催化性能,但当TiO2负载量过高时,CFA上的TiO2在水处理过程中容易脱落,对TiO2/CFA光催化剂的重复使用性能不利.本研究中,最佳的TiO2负载量约为50%,循环使用6次,其光催化降解效率没有明显降低,双氯芬酸钠的降解率均可达70%以上.