重点流域水系沉积物中多环芳烃标准样品制备

环境标准样品是监测过程中重要的质量控制手段,中国受天然基体标准样品制备技术的制约,尚未拥有自己的沉积物中多环芳烃标准样品。为制备符合中国重点流域沉积物类型及多环芳烃浓度水平的沉积物标准样品,对中国6个重点流域的沉积物进行了采样,获得了制备多环芳烃标准样品的原料。分析常温及冷冻2种干燥方式对多环芳烃的影响,为制备大批量多环芳烃标准样品提供数据支持。对11个点位样品采用气相色谱质谱法测定16种优控多环芳烃化合物浓度,结果表明,样品均匀性良好,样品中多环芳烃检出率在99%以上,江河沉积物样品中多环芳烃浓度区间为664~2.91×103μg/kg,湖泊样品最高值达到1.25×105μg/kg,其主要污染源是化学燃料的燃烧。为中国制备水系沉积物中多环芳烃标准样品积累了技术基础。     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

氨气敏电极法和纳氏试剂分光光度法对地表水中氨氮的比对测试

采用不同质量浓度的氨氮标准样品和实际样品,用氨气敏电极法和纳氏试剂分光光度法进行同步测试。结果表明,2种分析方法在水样氨氮质量浓度在0. 159～2. 81 mg/L范围内具有良好的可比性、精密性和准确性。氨气敏电极法的检出限为0. 03 mg/L,平行6次测定样品的相对标准偏差为0. 4%～4. 2%,加标回收率为85. 0%～110%;纳氏试剂分光光度法的检出限为0. 025 mg/L,平行6次测定样品的相对标准偏差为0. 5%～6. 4%,加标回收率为93. 0%～99. 8%。同时氨气敏电极法在样品预处理、试剂配制和分析时间上要优于纳氏试剂分光光度法。氨气敏电极法能够满足地表水自动监测在线比对实际工作的需求,该方法具有良好的适用性。     

黑龙江省平水期地表水总磷构成的研究

通过对黑龙江省平水期地表水总磷监测结果分析,探讨地表水总磷的构成、成因;提出了从源头治理地表水总磷污染建议。     

黄土沉积物中次生细粒强磁性矿物记录的古气候信息

伊犁地区位于我国新疆地区西北部,为天山山脉环绕。区内降水自西向东递增,而温 度则由于海拔高度的抬升而逐渐降低。上述地理环境有利于分析和探讨温度和降水与黄土沉积 物中次生细粒强磁性颗粒数量之间关系。本研究在伊犁河谷西部地区,对不同海拔高度黄土表 层沉积物进行样品采集。环境磁学分析结果显示：黄土沉积物中次生细粒强磁性矿物含量与降 水量之间存在很好的正相关关系,而与温度之间存在反相关关系。结合黄土高原的研究结果可 以发现：温度对黄土沉积物中次生细粒强磁性矿物的数量影响微弱,降水是控制其含量的主要 因素;即：在黄土古气候研究中,次生细粒强磁性矿物的磁化率可以作为古降水量的代用指标, 但对温度变化不敏感。     

抚仙湖沉积物重金属垂向分布及潜在生态风险评价

基于环境放射性核素210Pbex和137 Cs计年法确定抚仙湖北、中和南部三个沉积物柱芯的沉积年代,分析了各个柱芯近150年的重金属(Cr、Cu、Zn、As和Pb)的垂向分布特征,并用潜在生态风险指数法进行了潜在生态风险分析。结果表明,抚仙湖不同湖区沉积物重金属的垂向分布存在明显差异,其中Zn、As和Pb呈现整体向上增加的趋势,Cr和Cu分别呈现微波动变化和下降趋势。重金属元素之间相关性表明Zn、As和Pb具有较好的同源性,而Cr和Cu来源不同。重金属元素与营养盐TP之间呈较好的相关性,与TN和TOC则相关性较差或无相关性存在。潜在生态风险指数评价显示近150年来抚仙湖不同湖区沉积物重金属污染水平差异明显,其中北部和南部As是主要的生态风险贡献因子,而中部Cu是主要的生态风险贡献因子。抚仙湖中部和南部沉积物重金属总体处于中等生态风险,而北部沉积物重金属由中等上升为较高生态风险出现在20世纪90年代末期。     

海州湾表层沉积物重金属的来源特征及风险评价

根据2009年12月海州湾海域17个站位的环境调查资料,通过地统计学方法分析表层沉积物中6种重金属(Cd、As、Cu、Pb、Cr、Zn)的来源特征,采用潜在生态风险指数法进行重金属风险评价.结果表明,重金属分布格局整体呈西南高东北低、随离岸距离增大而减小的趋势;陆源污染输入是海州湾海域重金属的重要污染来源;有机碳含量、底质粒径和硫化物是影响重金属含量及其分布的重要因素;风险评价显示海州湾沉积物重金属总体处于中等生态风险状况,风险相对较高主要分布在龙王河口到临洪河口的近岸海域,潜在生态风险指数Cd>As>Cu>Pb>Cr>Zn,Cd是主要的生态风险贡献因子.     

Predicting the aquatic risk of realistic pesticide mixtures to species assemblages in Portuguese river basins

Although pesticide regulatory tools are mainly based on individual substances, aquatic ecosystems are usually exposed to multiple pesticides from their use on the variety of crops within the catchment of a river. This study estimated the impact of measured pesticide mixtures in surface waters from 2002 and 2008 within three important Portuguese river basins (‘Mondego’, ‘Sado’ and ‘Tejo’) on primary producers, arthropods and fish by toxic pressure calculation. Species sensitivity distributions (SSDs), in combination with mixture toxicity models, were applied. Considering the differences in the responses of the taxonomic groups as well as in the pesticide exposures that these organisms experience, variable acute multi-substance potentially affected fractions (msPAFs) were obtained. The median msPAF for primary producers and arthropods in surface waters of all river basins exceeded 5%, the cut-off value used in the prospective SSD approach for deriving individual environmental quality standards. A ranking procedure identified various photosystem II inhibiting herbicides, with oxadiazon having the relatively largest toxic effects on primary producers, while the organophosphorus insecticides, chlorfenvinphos and chlorpyrifos, and the organochloride endosulfan had the largest effects on arthropods and fish, respectively. These results ensure compliance with European legislation with regard to ecological risk assessment and management of pesticides in surface waters.     

Fabrication of ion doped WO3 photocatalysts through bulk and surface doping

Na⁺ doped WO₃ nanowire photocatalysts were prepared by using post-treatment (surface doping) and in situ (bulk doping) doping methods. Photocatalytic degradation of Methyl Blue was tested under visible light irradiation, the results showed that 1 wt.% Na⁺ bulk-doped WO₃ performed better, with higher photoactivity than surface-doped WO₃. Photoelectrochemical characterization revealed the differences in the photocatalytic process for surface doping and bulk doping. Uniform bulk doping could generate more electron–hole pairs, while minimizing the chance of electron–hole recombination. Some bulk properties such as the bandgap, Fermi level and band position could also be adjusted by bulk doping, but not by surface doping.     

固相萃取-超高效液相色谱/三重四极杆质谱法同时测定地表水中8种亚硝胺类化合物

建立了固相萃取（SPE）-超高效液相色谱/三重四极杆串联质谱（UPLC-MS/MS）同时测定地表水中8种亚硝胺类化合物的方法。水样中目标物经椰壳活性炭固相萃取小柱吸附富集，小柱经氮气吹干后采用二氯甲烷洗脱。待测样品采用Atlantis T₃柱，以水-甲醇作为流动相进行梯度洗脱，大气压力化学电离源（APCI）正离子模式多反应监测方式（MRM）进行检测，内标法定量分析。8种目标物在相关线性范围内线性良好(r≥0.9950)，地表水加标回收率为55.4%~90.4%，相对标准偏差为3.1%~14.3%，方法检出限为1.1 ~1.8 ng/L。本方法准确度和灵敏度高，适用于快速测定地表水中8种亚硝胺类化合物含量。