Hexabromocyclododecanes in surface sediments and a sediment core from Rivers and Harbor in the northern Chinese city of Tianjin

In the present study, hexabromocyclododecanes (HBCDs) were investigated in the sediment from Haihe River (HR), Dagu Dainage Canal (DDC) and Tianjin Harbor (TH) at Bohai Bay using a total of 51 samples of surface sediments and a sediment core collected from May to September in 2010, and its diastereomer- and enantiomer-specific profiles were analyzed. The concentration of total HBCDs were generally high, with mean value and ranges of 31.0 and 1.35–634 ng g^?1 dw, respectively. The contamination followed the order of TH > DDC > HR. Higher levels (up to 634 ng g^?1 dw) occurred in the lower reach of HR and DDC located in an industrial area of Tianjin. This is the first time to report so high concentration of HBCDs in sediment in Southeast Asia. The γ-diastereomer dominated in most samples (44 out of 51), and this is in agreement with the diastereomer distribution pattern in industrial products, while α-HBCD was the dominant diastereomer in the other seven samples. However, only few samples exhibited γ-diastereomer ratio similar to that (75–89%) in technical products, indicating the inter-transformation and variable degradation of the different isomers. The high ratio of γ-diastereomer could be used as an indicator for fresh contamination input. Enantiomeric factors (EFs) of HBCD isomers in most of the samples were statistically different from technical products (p < 0.05), showing a trend of more easily enrichment of the (?)-HBCD-enantiomer compared to the (+)-HBCD-enantiomer. The δ- and ε-diastereomers were frequently detected but at low level. The HBCDs in the sediment core showed several peaks, and the greatest value occurred in 2005, when a plastic manufacture plant using HBCD was set up nearby.     

Hexabromocyclododecanes in limnic and marine organisms and terrestrial plants from Tianjin,China: Diastereomer- and enantiomer-specific profiles,biomagnification, and human exposure

To interpret the distribution of hexabromocyclododecanes (HBCDs) in various organisms, we measured the concentrations and diastereomer and enantiomer profiles of HBCDs in 21 different species of limnic and marine cohorts from Tianjin, China. The concentration ranges of HBCDs in limnic and marine organisms were 64.3–1111 ng g⁻¹ lw and 85.5–989 ng g⁻¹ lw, respectively. Living habitat and feeding habits had important impacts on HBCD diastereomer distribution. Most of the species appeared to preferentially select (+)-α-, (−)-β- and (−)-γ-HBCD. There is a tendency that the total and α-HBCDs were magnified as trophic level increased with trophic magnification factors (TMFs) around 2. The concentrations of HBCDs in the limnic and marine fishes were highest in the liver, followed by the gill, skin, and muscle. In terrestrial plants, the highest concentrations of HBCDs were observed in the leaf, followed by the root and the rhizosphere soil. Plants showed enantioselectivity for HBCD enantiomers, which varied with plant species and organs (leaf vs. root) of the same plant. Higher estimated daily intakes (EDIs) of HBCDs were observed from fish than from wheat.     

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in biosolids from municipal wastewater treatment plants in China

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) along with methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have been frequently identified as natural compounds in marine environment and also assumed as metabolites of PBDEs. In the present study, nine OH-PBDE, nine MeO-PBDE and 10 PBDE congeners were studied in the sewage sludge collected from 36 municipal wastewater treatment plants (WWTPs) in 27 cities of China. The results suggest that OH-PBDEs and PBDEs are ubiquitous in sewage sludge in China, however, methoxylated PBDEs were not detectable. Composition profiles of detected OH-PBDE congeners were different depending on the sampling location. ΣOH-PBDEs in WWTPs sludge ranged from 0.04 to 2.24 ng g^?1 dry weight (mean: 0.35 ng g^?1 dry weight). The total amount of the two most prominent congeners (6-OH-BDE-47 + 2′-OH-BDE-68) accounted for about 53.3–100% of the sum of all six identified congeners. A significant linear relationship was found between 6-OH-BDE-47 and 2′-OH-BDE-68. A distinct geographical distribution of ΣOH-PBDEs was observed with greater concentrations of OH-PBDEs at coastal areas than inland regions in China.     

生物填料地下渗滤系统对生活污水的脱氮

将草甸棕壤、炉渣和活性污泥等基质按体积比13∶6∶1配制生物填料,研究了生物填料地下渗滤系统（subsurface wastewater infiltration system,SWIS）在不同的水力负荷和污染负荷条件下对校园生活污水的脱氮效果。场地实验结果表明,当BOD5负荷为12.0 g BOD5/（m2·d）,表面水力负荷为0.04-0.10 m3/（m2·d）时,SWIS对NH＋4-N和TN的平均去除率分别为92.4%和82.0%。当水力负荷为0.08 m3/（m2·d）,BOD5负荷9.3-16.8 g BOD5/（m2·d）时,SWIS对NH＋4-N和TN的平均去除率为92.7%和81.2%。SWIS中氧化还原电位（oxygen reduction potential,ORP）随进水水力负荷和BOD5负荷的增加而降低,脱氮效率下降。综合出水水质和处理效率,适宜的水力负荷和污染负荷分别为0.065 m3/（m2·d）和12.0 g BOD5/（m2·d）。在此条件下,SWIS的启动周期为25-30 d。出水水质均优于《城市污水再生利用-景观环境用水水质》（GB/T18921-2002）标准,且处理效果稳定,抗负荷冲击能力强。     

矿化垃圾床＋三维电极／电Fenton法处理老龄垃圾渗滤液

提出以二级矿化垃圾床为预处理单元,串联三维电极／电Fenton处理老龄垃圾渗滤液的组合工艺。矿化垃圾床处理后渗滤液中COD、氨氮、总磷、色度的去除率分别为80．55％、88．47％、98．32％和87．53％。通过单因素实验和正交实验,确定了三维电极／电Fenton法最佳工艺条件。经该组合工艺后,渗滤液中COD、氨氮、总磷和色度的最高去除率分别可达97．08％、95．24％、99．55％和96．92％,其中COD、总磷、色度这3个指标低于《生活垃圾填埋场污染控制标准》（GB16889．2008）表2规定的排放标准,为该组合工艺在实际中的应用提供重要理论依据。     

季节性城市生活垃圾成分分析及厌氧消化特性研究

城市生活垃圾的成分及特性随着季节和人类在不同季节的生活习惯而变化,针对我国北方城市研究了一年中不同季节的城市生活垃圾成分特点,对影响厌氧发酵过程的相关成分如总有机碳（TOC）、总氮（TN）、蛋白质、脂肪和还原糖等进行了测定分析。通过厌氧消化实验,测得不同季节城市生活垃圾pH值、日产气量、沼气甲烷含量、甲烷累积量、挥发性脂肪酸（VFAs）和氧化还原电位（ORP）等参数的变化规律,分析相应变化的影响因素。结果表明,二、三季度的含水率分别为64．81％和67．50％,高于一、四季度,一季度发酵原料中蛋白质和脂肪含量分别为12．56％和8．86％,明显高于其他3个季度。一季度甲烷累积量最高,达到17616mL,单位发酵原料的产气量为204．8mL／g,也是4个季度中最高的,说明蛋白质、脂肪等有机成分含量对厌氧发酵过程及结果影响比较明显。为进一步的城市生活垃圾厌氧消化制取生物燃气的工艺条件提供依据。     

两种AHLs信号分子对生物膜法养殖污水处理条件下水体内环境的影响

为提高生物膜法处理养殖污水的效果,对不同信号分子条件下的生物膜处理情况进行研究。在室内循环水养殖系统中,设定3个实验组和1个对照组,分别添加乙醇、C6-HSL、N-3-oxo-C8-HSL和蒸馏水,并在模拟过程中取样分析。实验结果表明,3个实验组附着基上的生物量明显多于对照组,尤其是添加N-3-oxo-C8-HSL组产生的生物量约为对照组的6倍;经添加C6-HSL和N-3-oxo-C8-HSL处理的养殖水体中,亚硝酸盐最终浓度比对照组低28.6%,但无机磷浓度稍高。数据因子分析结果表明,实验过程中(9～27 d),添加AHLs信号因子C6-HSL和N-3-oxo-C8-HSL两组养殖水体内环境的总体得分较高,说明养殖水体的内环境处于较好状态。     

响应面法优化聚丙烯酸/腐殖酸/累托石吸附剂的制备条件

以累托石、丙烯酸及腐殖酸为原料制备出能同时吸附重金属和多环芳烃的吸附剂聚丙烯酸/腐殖酸/累托石,采用响应面试验设计法优化吸附剂的制备条件。利用Design Expert软件,建立了预测吸附剂对Cd2+、菲吸附量的二次回归模型,对回归模型进行了方差分析,并确定了吸附剂的最佳制备条件。结果表明,二次回归模型能较好地模拟Cd2+、菲的吸附量与影响因子丙烯酸中和度、引发剂量和交联剂量之间的关系。各因子对Cd2+吸附量的影响次序为:交联剂量>引发剂量>丙烯酸中和度;对菲吸附量的影响次序为引发剂量>交联剂量>丙烯酸中和度。吸附剂的最佳制备条件为:累托石、丙烯酸和腐殖酸三者的质量比为65∶30∶5,丙烯酸中和度、引发剂量和交联剂量分别为75.16%、2.57%和0.44%。在此优化条件下制备的吸附剂对Cd2+和菲的吸附量分别为170.19 mg/g和7.36 mg/g。     

4种人工湿地基质对马拉硫磷的吸附特性

通过基质对马拉硫磷的等温吸附和吸附动力学实验,研究天然土壤、煤渣、沸石、砾石对马拉硫磷的吸附特性,为人工湿地处理含马拉硫磷废水提供理论依据.结果表明:马拉硫磷浓度为2.25 ～ 90 mg/L条件下,Langmuir和Freundlich方程均能较好地拟合4种基质对马拉硫磷的等温吸附过程,并且Freundlich方程的拟合效果要好于Langmuir方程.马拉硫磷的理论饱和吸附量大小依次为天然土壤(9.9304 mg/g)＞煤渣(1.6173 mg/g)＞沸石(0.6039 mg/g)＞砾石(0.3965 mg/g).4种基质对马拉硫磷的缓冲能力大小依次为天然土壤＞煤渣＞沸石＞砾石,即当进水马拉硫磷浓度波动较大时,作为湿地基质天然土壤使人工湿地系统维持稳定出水水质的能力最强.马拉硫磷浓度为4.5 mg/L条件下,吸附动力学模型Elovich方程能较好地拟合4种基质对马拉硫磷的吸附动力学特征,说明4种基质对马拉硫磷的吸附是表面吸附和内部扩散吸附共同作用的结果.因此,天然土壤和煤渣适宜作为处理含马拉硫磷废水的人工湿地基质.     

铁炭微电解法降解TAIC废水

TAIC（三烯丙基异氰脲酸酯）作为过氧化物交联或自由基反应交联的助交联剂被广泛应用。由于TAIC性质稳定难于生物降解,采用铁炭微电解法处理TAIC生产废水,并考察了铁炭比、进水pH值、反应时间对处理效果的影响,以及TAIC降解机理和反应动力学过程。结果表明,影响微电解工艺的因素主次关系为：pH>Fe/C质量比>反应时间;在最佳条件进水pH值为5,铁炭质量比为2：1,反应时间为135 min时,COD的去除率达到46%以上,TAIC的去除率达到48%以上。TAIC去除机理研究表明,微电解对TAIC废水的作用主要通过·H的还原和铁离子的絮凝作用,其中·H的还原作用是TAIC降解的主要原因。反应动力学分析表明,铁炭微电解法处理TAIC的降解过程基本符合二级反应动力学规律,通过建立模型并拟合出了TAIC降解的二级反应动力学方程。