聚硅酸对不同形态铝沉积行为的影响

针对给水管网中残余铝沉积和再溶解现象可能引起的水质问题,研究了聚硅酸对不同水解聚合形态铝沉积、再溶解的影响,并以石英微晶天平为表征手段,初步探讨了聚硅酸对不同形态铝沉积、再溶解过程影响的机理.结果表明,聚硅酸能显著改变不同水解聚合形态铝的沉积、再溶解行为.聚硅酸可与3种水解聚合形态的铝迅速结合而生成可沉积产物,但产物性质不同.以单体形态为主的Al_0与聚硅酸的反应产物性质较稳定,部分以溶解态存在,部分以非溶解态(可沉积态)存在;尽管铝的两种聚合形态Al_(13)和Al_(30)与聚硅酸反应也生成了部分可沉积产物,但随着时间的推移,这些产物又逐渐向溶解态转化.铝硅比对Al_0体系中铝的沉积溶解行为影响较小,而对Al_(13)和Al_(30)影响较大,且在0.2∶20(以Al和SiO_2计的质量比)时,沉积态铝的溶解速率最快.     

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

Carbonyl emissions from heavy-duty diesel vehicle exhaust in China and the contribution to ozone formation potential

Fifteen heavy-duty diesel vehicles were tested on chassis dynamometer by using typical heavy duty driving cycle and fuel economy cycle. The air from the exhaust was sampled by 2,4- dinitrophenyhydrazine cartridge and 23 carbonyl compounds were analyzed by high performance liquid chromatography. The average emission factor of carbonyls was 97.2 mg/km, higher than that of light-duty diesel vehicles and gasoline-powered vehicles. Formaldehyde, acetaldehyde, acetone and propionaidehyde were the species with the highest emission factors. Main influencing factors for carbonyl emissions were vehicle type, average speed and regulated emission standard, and the impact of vehicle loading was not evident in this study. National emission of carbonyls from diesel vehicles exhaust was calculated for China, 2011, based on both vehicle miles traveled and fuel consumption. Carbonyl emission of diesel vehicle was estimated to be 45.8 Gg, and was comparable to gasolinepowered vehicles （58.4 Gg）. The emissions of formaldehyde, acetaldehyde and acetone were 12.6, 6.9, 3.8 Gg, respectively. The ozone formation potential of carbonyls from diesel vehicles exhaust was 537 mg O3/km, higher than 497 mg O3/km of none-methane hydrocarbons emitted from diesel vehicles.     

Phytoremediation of levonorgestrel in aquatic environment by hydrophytes

Adsorption and degradation of levonorgestrel （LNG） by two hydrophytes, Cyperus alternfolius （CA） and Eichhornia crassipes （EC）, were investigated under light-shielding conditions in the water column. Variations of LNG concentrations in water, plant root epidermis, root, stem and leaf of the plants were analyzed. The results indicated that the removal efficiency of LNG by hydrophytes over the period of 50 days was significantly greater than the blank control （p 〈 0.05）, with the removal rates of 79.80%± 3.10% and 78.86% ± 2.55% for CA and EC, respectively. Compared with bio-adsorption, bio-conversion of LNG was found to be the dominant elimination pathway, evidenced by relatively high conversion rates （77.31% ±2.68% for CA and 77.82% ± 2.95% for EC）, while the adsorption rates were lower （1.77% ± 0.90% for CA and 1.05% ± 0.40% for EC）. The bio-adsorption and conversion of LNG showed no significant differences between the two hydrophytes. Additionally, the mineralization on root epidermis played an important role in the reduction of LNG in water.     

钦州湾无机氮入海通量及其富营养化症状分析

根据对环钦州湾区域的入海河流、直排海污染源及养殖废水无机氮入海通量的估算,2011年钦州湾无机氮入海通量约为7 655 t,其中入海河流无机氮入海通量占总量的96.4%,直排海污染源次之。入海无机氮占钦州湾无机氮总量的比重为36.7%,说明钦州湾已属中等强度人为影响海域。根据对钦州湾富营养化症状——叶绿素a含量的分析,钦州湾富营养化症状不明显,钦州湾整体的富营养化程度较低。因而仅以营养盐含量评价目标海域的富营养化程度,易失之偏颇,宜结合富营养化症状来判断目标海域的富营养化程度。     

三峡水库沉积物中碱性磷酸酶的活性

为了解三峡水库沉积物中碱性磷酸酶(APA)活性的特点,采集了来自三峡水库干支流的11个柱状沉积物,测定了沉积物中碱性磷酸酶的活性。结果表明,三峡水库沉积物中碱性磷酸酶活性有明显的空间异质性。干流的茅坪、郭家坝、巴东的酶活性小且没有显著性差异,茅坪位点的碱性磷酸酶活性在垂直方向上随着采样深度的增加而递减,而巴东和郭家坝的酶活性在垂直方向上变化趋势不明显;支流酶活性表现为:香溪河>大宁河>小江>干流,从上游到下游的酶活性变化呈现多峰值的变化,而在垂直方向上同样表现为随着采样深度的增加而递减。此外,碱性磷酸酶活性与水体富营养化程度、沉积物的污染程度和沉积环境有关,因此可以将其作为评价水体营养状况的指标之一。     

再悬浮过程中河流底泥PAHs的迁移与释放

利用再悬浮模拟(particle entrainment simulator,PES)装置模拟了河流底泥在受到上层扰动力后的再悬浮过程.结果表明,沉积物性质如粒径组成及PAHs含量对沉积物再悬浮过程中PAHs的释放影响显著.再悬浮过程中上覆水体总悬浮颗粒物(total suspended solids,TSS)含量与颗粒态PAHs之间存在极显著相关关系.切应力对再悬浮过程中PAHs释放的影响体现在两方面.一方面,单位体积的颗粒态PAHs随切应力增大而增大;另一方面,悬浮颗粒上PAHs的富集效应随切应力增大而减弱,是由于切应力强烈导致吸附作用弱的大颗粒进入水体.上覆水体中的PAHs总量在一段时间上升后于120 min或240min趋于稳定,而颗粒态与溶解态之间具有良好响应.高低环PAHs释放行为差异显著,由于中高环PAHs的疏水性,上覆水体中检测到的多为3~4环个体.     

滴水湖及其水体交换区沉积物和土壤中PAHs的分布及生态风险评价

采用GC-MS联用技术分析了滴水湖及其水体交换区23个表层沉积物和土壤中16种多环芳烃(PAHs)的含量,探讨其分布特征及来源并对其生态风险进行评价.结果表明,滴水湖沉积物中16种PAHs含量范围是11.49~157.09 ng·g-1,平均含量为66.60 ng·g-1,湖区沉积物中PAHs含量比入湖区低,但比出湖区高.湖区外的沉积物和土壤中PAHs组成主要以中、高分子量PAHs(4环、5~6环)为主,而湖区内表层沉积物中PAHs组成则以低分子量PAHs(2~3环)和高分子量PAHs(5~6环)为主.通过特征化合物分子比值法、主成分分析及多元线性回归模型判源,表明湖区外沉积物和土壤中PAHs来源主要为燃烧源,而湖区内沉积物中PAHs来源为燃烧源和石油类产品泄漏的混合来源.生态风险评价显示,滴水湖及其水体交换区沉积物和土壤中PAHs生态风险较低.     

基于非点源溶解态氮负荷估算的率水流域土地利用结构优化研究

利用区域营养盐管理模型(ReNuMa)对率水流域2000~2010年的溶解态氮(DN)负荷进行了定量估算和来源解析.在率定期和验证期,径流和DN负荷模拟的Ens和R2都大于0.9,模型具备可靠的模拟能力.结果表明,率水流域的年均非点源DN负荷为1.11×103t·a-1,负荷强度为(0.75±0.22)t·km-2.在所有土地利用类型中,水田的DN负荷强度最大[28.60kg·(hm2·a)-1],林地的DN负荷强度最小[2.71 kg·(hm2·a)-1].农业生产用地(水田、谷物、经济作物、果园和茶园)对DN负荷的贡献最大,表明人类影响下的农业生产活动是流域非点源污染的最主要来源.基于污染负荷适量削减和农业经济产值最大化原则,开展了流域2015年土地利用结构优化分析,规划结果表明在土地利用结构最优情况下,经济收益的增长依然伴随着负荷的增加,但经济产值的增幅大于DN负荷的增幅.     

老化的生物质炭性质变化及对菲吸持的影响

将稻壳分别在350℃和550℃热解温度下制备成生物质炭,避光条件下恒温培养300 d,通过傅里叶变换红外光谱、扫描电镜和核磁共振等技术手段及平衡吸附实验,探究生物质炭老化前后的动态结构变化及对菲吸持作用的影响.结果表明,生物质炭老化过程中氧含量增加,含氧基团增多,对菲的非线性吸附行为显著增强.热解温度的不同决定了生物质炭老化过程中性质变化的差异,350℃热解的生物质炭,老化后极性增强,芳香性减弱,而550℃热解的生物质炭,老化后脂肪族碳类物质增加,羧基减少,芳香性增强,Langmiur预测的菲在350℃热解的生物质炭上老化前后的最大吸附量分别为3.57 mg·g-1、2.35mg·g-1,主要是老化后性质变化抑制了表面吸附作用,而550℃热解的生物质炭上老化前后的最大吸附量分别为0.42mg·g-1、4.17 mg·g-1,老化后吸附量的显著增加主要是生物质炭性质变化促进了对菲的分配作用与表面吸附作用.研究生物质炭在自然环境中的老化行为对环境污染物固定的稳定性有着重要意义.