东海沿岸贝类体内石油烃和有机氯农药的分布特征及评价

本研究分别于2006、2007年5月在东海沿岸海域22个站位采集牡蛎、贻贝、四角蛤蜊、文蛤、花蛤5种贝类样品，采用荧光分光光度法和气相色谱法检测贝类体内的石油烃（TPHs）和有机氯农药(HCHs和DDTs) 含量，分析东海沿岸海域贝类体内的TPHs、HCHs和DDTs的时空分布特征和HCHs、DDTs的组分特征，比较不同贝类体内污染物含量的差异，探讨HCHs和DDTs的来源，并对贝类进行初步海洋生物质量评价和人体健康风险评价。研究结果表明： （1）东海沿岸海域贝类体内TPHs含量范围为0.40 74.40 mg kg-1，平均含量为9.42 mg kg-1；HCHs含量为ND～5.42×10-3mg kg-1，平均含量为1.47×10-3 mg kg-1；DDTs含量为2.09×10-3～197.66×10-3mg kg-1，平均含量为38.05×10-3 mg kg-1。其中，TPHs含量在长江口及邻近海域较高， HCHs和DDTs含量在江苏省的如东、海门和浙江省的各海域含量较高。与2006年相比，2007年贝类体内TPHs含量与2006年基本持平，HCHs含量有稍微降低，但是DDTs含量有明显升高趋势。 （2）HCHs和DDTs组分分析表明，α-HCH和β-HCH占HCHs总量的绝大多数，γ-HCH和δ-HCH仅有极少量检出，大多数区域的α-HCH/γ-HCH比值在4-7之间，说明研究区域内有新的HCHs污染源； DDTs 中O,P’-DDT/P,P'-DDT的比值远高于工业DDTs中O,P’-DDT/P,P'-DDT的比值，分析认为其与周围区域使用三氯杀螨醇密切有关。 （3）贝类体内的TPHs、HCHs和DDTs与水体、沉积物中的相应有机物存在正相关性。相对于TPHs和HCHs，DDTs更容易在贝类体内富集；牡蛎对TPHs和HCHs、DDTs的累积能力明显高于四角蛤蜊和贻贝。 （4）质量评价显示TPHs在局部海域超标，HCHs未超标，DDTs含量超标严重。人体健康风险评估结果显示，东海沿岸海域贝类体内HCHs和DDTs的致癌风险和暴露风险均在可接受的范围之内，消费者因食用监测海域的贝类而受到HCHs和DDTs危害的可能性不大。 （5）与世界其他海域比较表明，东海海域贝类TPHs和HCHs含量处于中等水平， DDTs含量处于比较高的水平。

Persistent organic pollutant residues in the sediments and mollusks from the Bohai Sea coastal areas, North China: An overview

The Bohai Sea costal area is one of the most developed zones of China and the sewage water from populous and developed cities, including Beijing, Tianjin. Qinhuangdao and Dalian is discharged into the Bohai Sea. Additionally, its semi-enclosed characteristic restricts water exchange, which leads to high accumulation of pollutants in the environment. This overview presents the residues of 6 classes of Persistent Organic Pollutants (POPs). including PAHs, DDTs. HCHs, PCBs and PCDD/Fs. in the sediments and mollusks of the Bohai Sea through analyzing previous literatures. In the sediments. the highest PAH concentrations were detected in the vicinities of Qinhuangdao, while the northeast corner of the Bohai Bay possessed the highest levels of DDTs and PCBs. The investigations on HCHs and PCDD/Fs distributions on the whole sea scale have not been reported. In mollusks, PAH concentrations were in the same order of magnitude in the whole Bohai Sea, so were DDTs. HCHs and PCBs, while the outlier maximum values of PCDDs and PCDFs occurred in Yingkou. In general, the POPs residues in mollusks collected from Shandong Province were higher than the other areas. The compositions of DDTs, HCHs and PCBs in sediments indicated their recent usage. By comparing POP concentrations in sediments with the recommended criterions, it was shown that some individual PAH compounds occasionally associated with adverse biological effects in the vicinities of the Liaodong Bay and Qinhuangdao, and the Liaohe River Estuary were heavily contaminated with DDTs, but PCBs were all below the thresholds. In order to reveal the transference and transformation of POPs in the environment, further studies concerning with their behavior, fate and bioaccumulation in the different trophic levels should be programmed. Moreover, laws and regulations should be enforced to ban the illegal usage of POPs-containing pesticides to guarantee health of the environment and human. (C) 2008 Elsevier Ltd. All rights reserved.

Meat characteristics of Qinghai yak and semi-wild yak

Six domestic yaks aged 6 years, comprising three culling male and three culling female yaks, from the Qinghai Lake area and three male semi-wild yaks aged 6 months from Datong Yak Farm were used to detect the levels of amino acids, mineral elements, residual heavy metals and pesticides in yak meat. The results showed that there was little difference in amino acid levels for different types of yak by age and sex. The meat of the adult male yak was 7.35 mg/kg higher in calcium (P < 0.05) and 124 mg/kg higher in phosphorus (P < 0.01) than that of the adult female yak. There was an obvious difference in zinc content, and there was also a significant difference for copper and sulfur between adult male and female yaks (P < 0.01). Iron was 8.85 mg/kg higher in semi-wild yaks than in domestic yaks, but there were no differences for other minerals. The levels of residual heavy metals and residual pesticides were well within those allowed by the National Standard of China. Furthermore, the data showed that introducing wild yak's blood did not result in a quality change in the domestic yak meat. Yak meat from Qinghai Plateau has the characteristics of being non-polluted and rich in amino acids in comparison with local yellow cattle meat.

Oxidative destruction of chlorobenzene and o-dichlorobenzene on a highly active catalyst: MnOx/TiO2-Al2O3

A highly active catalyst, MnOx/TiO2-Al2O3, was prepared by impregnating MnOx species on TiO2-modified Al2O3. The TiO2 species in TiO2-Al2O3 support is in a monolayer dispersion, and the MnOx species is again highly dispersed on TiO2-Al2O3 Support. The total oxidation of chlorobenzene and o-dichlorobenzene on MnOx/TiO2-Al2O3 catalyst can be achieved at 300 degreesC and 250 degreesC respectively, at the space velocity of 8000 h(-1). The activity of MnOx/TiO2-Al2O3 catalyst (Mn loading 11.2 wt%) is gradually increased in the first 10-20 h and then keeps stable at least for the measured 52 h at 16,000 h(-1). Furthermore, no chlorinated organic byproducts are detected in the effluent during the oxidative destruction of chlorobenzene and o-dichlorobenzene. It is proposed that the partially chlorinated and highly dispersed manganese oxide on a monolayer TiO2-modified Al2O3 is responsible for the high and stable activity for the total oxidation of chlorinated aromatics. (C) 2001 Academic Press.

Catalytic oxidation of chlorobenzene on supported manganese oxide catalysts

Total oxidation of chlorinated aromatics on supported manganese oxide catalysts was investigated. The catalysts have been prepared by wet impregnation method and characterized by XRD and TPR. Among the catalysts with the supports of TiO(2), Al(2)O(3) and SiO(2), titania supported catalyst (MnO(x)/TiO(2)) gives the highest catalytic activity. MnO(x)/TiO(2) (Mn loading, 1.9 wt.%) shows the total oxidation of chlorobenzene at about 400 degreesC. The activity can be stable for over 82 h except for the first few hours. At lower Mn loadings for MnO(x)/TiO(2), only one reduction peak appears at about 400 degreesC due to the highly dispersed manganese oxide. With the increase of Mn loading, another reduction peak emerges at about 500 degreesC, which is close to the reduction peak of bulk Mn(2)O(3) at 520 degreesC. TPR of the used catalyst is totally different from that of the fresh one indicating that the chemical state of the active species is changed during the chlorobenzene oxidation. The characterization studies of MnO(x)/TiO(2) showed that the highly dispersed MnO(x) is the precursor of the active phase, which can be converted into the active phase, mainly oxychlorinated manganese (MnO(y)Cl(z)), under working conditions of chlorobenzene oxidation. (C) 2001 Elsevier Science B.V. All rights reserved.

A practical approach to the degradation of polychlorinated biphenyls in transformer oil

A practical and efficient disposal method for hydrodechlormation of polychlorinated biphenyls (PCBs) in transformer oil is reported. Transformer oil containing PCBs was treated by nanometric sodium hydride (nano-NaH) and transition metal catalysts. High destruction and removal efficiency (89.8%) can be attained by nano-NaH alone under mild conditions. The process exhibits apparent characteristics of a first order reaction. The reductive ability of nano-NaH was enhanced by the addition of transition metal catalysts. In the presence of TiCl4, 99.9% PCBs was hydrodechlorinated. The complex reducing reagents, Ni(OAc)(2) + i-PrONa, show extra hydrodechlorinating activity for di-chlorinated biphenyls. (c) 2004 Elsevier Ltd. All rights reserved.

Development and application of a sol-gel immunosorbent-based method for the determination of isoproturon in surface water

An immunosorbent was fabricated by encapsulation Of monoclonal anti-isoproturon antibodies in sol-gel matrix. The immunosorbent-based loading, rinsing and eluting processes were optimized. Based on these optimizations, the sol-gel immunosorbent (SG-IS) selectively extracted isoproturon from an artificial mixture of 68 pesticides. In addition to this high selectivity, the SG-IS proved to be reusable. The SG-IS was combined with liquid chromatography-tandem mass spectrometry (LC-MS-MS) to determine isoproturon in surface water, and the linear range was up to 2.2 mu g/l with correlation coefficient higher than 0.99 and relative standard deviation (RSD) lower than 5% (n = 8). The limit of quantitation (LOQ) for 25-ml surface water sample was 5 ng/l. (c) 2006 Elsevier B.V. All rights reserved.