沈阳市大气PM2.5中水溶性离子的季节变化特征

为研究沈阳市大气中PM2.5及其水溶性离子的污染特征、季节差异和来源情况,使用URG-9000D在线监测系统对沈阳市2019年大气颗粒物进行连续的采样分析,并利用正交矩阵因子分析法(PMF)进行污染物的来源解析.结果 表明,2019年沈阳市秋冬季节PM2.5质量浓度变化受相对湿度影响较大,冬季PM2.5平均质量浓度达到85.76 μg·m-3,细粒子污染较为严重.沈阳市大气PM2.5中SNA(SO42-、NO3和NH4+)所占比重表现为春季最高秋季最低;夏季SO42-和NH4+浓度较高,而NO3-浓度较低.SO42-在夏季呈单峰型日变化,与NO3-变化趋势相反.春夏秋三季NH4+与SO42-、NO3-主要结合为(NH4)2SO4和NH4NO3,冬季NH4+主要以(NH4)2SO4和NH4HSO4的形式存在.沈阳市存在较强的SO2和NOx二次转化现象,且各季节中SO2的转化率均高于NO2.PMF源解析结果表明,二次源对沈阳市大气污染贡献最大,夏秋季生物质燃烧和冬季燃煤源贡献同样不可忽视.     

How aerosol direct effects influence the source contributions to PM2.5 concentrations over Southern Hebei,China in severe winter haze episodes

The aerosol direct effects result in a 3%–9% increase in PM_2.5 concentrations over Southern Hebei. These impacts are substantially different under different PM_2.5 loadings. Industrial and domestic contributions will be underestimated if ignoring the feedbacks. Beijing-Tianjin-Hebei area is the most air polluted region in China and the three neighborhood southern Hebei cities, Shijiazhuang, Xingtai, and Handan, are listed in the top ten polluted cities with severe PM_2.5 pollution. The objective of this paper is to evaluate the impacts of aerosol direct effects on air quality over the southern Hebei cities, as well as the impacts when considering those effects on source apportionment using three dimensional air quality models. The WRF/Chem model was applied over the East Asia and northern China at 36 and 12 km horizontal grid resolutions, respectively, for the period of January 2013, with two sets of simulations with or without aerosol-meteorology feedbacks. The source contributions of power plants, industrial, domestic, transportation, and agriculture are evaluated using the Brute-Force Method (BFM) under the two simulation configurations. Our results indicate that, although the increases in PM_2.5 concentrations due to those effects over the three southern Hebei cities are only 3%–9% on montly average, they are much more significant under high PM_2.5 loadings (~50 μg·m⁻³ when PM_2.5 concentrations are higher than 400 μg m⁻³). When considering the aerosol feedbacks, the contributions of industrial and domestic sources assessed using the BFM will obviously increase (e.g., from 30%–34% to 32%–37% for industrial), especially under high PM_2.5 loadings (e.g., from 36%–44% to 43%–47% for domestic when PM_2.5>400 μg·m⁻³). Our results imply that the aerosol direct effects should not be ignored during severe pollution episodes, especially in short-term source apportionment using the BFM.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

苦马豆素致糖基转移酶活性改变对小鼠生殖激素分泌的影响

苦马豆素是疯草主要有毒成分,抑制α-甘露糖苷酶的活性,引起N-聚糖加工过程失调。笔者课题组前期研究得出:苦马豆素致糖蛋白激素(促卵泡素和促黄体素)糖基化位点上糖链结构发生改变,引起促性腺激素功能发生改变。而苦马豆素中毒对家畜生殖激素分泌的调节机制尚不明确。苦马豆素腹腔注射对小鼠进行染毒,收集妊娠期和分娩期小鼠的血液、子宫和卵巢组织,检测糖基转移酶活性、生殖激素水平及其受体mRNA和类固醇限速酶蛋白质表达量。结果表明:在妊娠和分娩期,苦马豆素致子宫内膜固有层大量低聚糖蓄积,显著抑制N-聚糖加工过程关键糖基转移酶的活性(P0.05);染毒组小鼠血液的生殖激素包括促卵泡素(FSH)、促黄体素(LH)、雌激素(E2)和孕酮(P4)水平显著低于对照组(P0.05)。在整个妊娠周期,染毒组小鼠4种激素受体mRNA的表达量显著低于对照组(P0.05)。在妊娠后期,染毒组小鼠3-β羟基类固醇脱氢酶(3-βHSD)和芳香化酶(CYP19A1)蛋白表达量显著低于对照组(P0.05)。苦马豆素可使N-聚糖加工紊乱,引起促性腺激素分泌降低,进一步降低生殖激素受体和性类固醇激素限速酶的表达量,致使性类固醇激素分泌下降,导致生殖激素分泌紊乱,最终结果造成机体繁殖性能下降。     

施用牛粪对As污染稻田水稻As吸收的影响

为探究牛粪施肥对污染稻田水稻As吸收的影响,采用盆栽培养试验研究了施加牛粪对土壤Fe和As的活性、水稻根表铁膜形成及籽粒As含量的影响。实验所用受高As矿山废水污染土壤(As:92. 3 mg/kg)施加10%～30%的牛粪,土壤溶解性有机碳含量增加8. 41～24. 5 mg/kg,土壤孔隙水pH提高0. 14～0. 59,土壤氧化还原电位降低93. 5～174 m V,与背景土(As:18. 1 mg/kg)变化趋势相同;施用牛粪还会活化土壤中的Fe和As,污染土壤Fe(II)、AO-Fe和HCl-As含量分别增加13. 5%～149%、35. 9%～90. 9%和70. 1%～181%,分别为背景土壤的0. 86～1. 66倍、1. 17～2. 15倍、4. 29～8. 91倍;施加牛粪能促进根表铁膜的形成,拔节期污染土壤和背景土壤水稻根表Fe分别是其对照的1. 56～1. 96倍和2. 09～3. 07倍,根表吸附As含量是其对照的3. 04～5. 18、3. 82～4. 08倍,根表附着Fe随牛粪的增加先增加后降低,至成熟期污染土壤水稻根表吸附Fe和As分别是背景土壤的1. 35～2. 91和8. 45～16. 6倍,根表As和Fe的物质量比为污染区(3. 49×10~(-3)～3. 55×10~(-3))背景区(4. 41×10~(-4)～6. 17×10~(-4));背景土壤施加牛粪后水稻籽粒As含量降低,最大降低36. 4%,而污染土壤水稻籽粒As含量增加,最大增加127%。牛粪对土壤As、Fe的活性及根表铁膜的形成都具有重要影响,会提高污染稻田籽粒中As的含量,含As矿山废水污染稻田应当谨慎施用牛粪。     

Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.     

镜泊湖流域浮游植物群落及其功能类群的时空演替特征研究

为了解镜泊湖流域浮游植物群落的时空变化特征,于2013年对镜泊湖流域进行了采样调查.共检测出浮游植物7门81种(属),以硅藻和绿藻为主,分属17个功能类群.时间上,春季浮游植物丰度、叶绿素含量和功能类群丰度均高于秋季.空间上,春季镜泊湖流域浮游植物丰度和叶绿素含量湖泊区＞汇水区＞出水区,秋季汇水区＞湖泊区＞出水区.多维尺度分析表明,镜泊湖流域不同区域之间浮游植物群落组成存在显著的空间差异.     

Different exposure levels of fine particulate matter and preterm birth: a meta-analysis based on cohort studies

The previous studies estimated the association between PM_2.5 (particulate matter with aerodynamic diameter less than or equal to 2.5 μm) exposure during pregnancy and preterm birth, only considered and highlighted the hazard effects of high levels of air pollutant exposure, and underestimated that low levels of pollutant exposure might also affect pregnancy outcome. We conducted a meta-analysis of 11 cohort studies, a total of more than 1,500,000 subjects. The results of these studies were pooled by exposure levels and study periods. PM_2.5 exposure during pregnancy was positively associated with preterm birth (OR = 1.15, 95% CI = 1.07–1.23), and during the first trimester of pregnancy, low levels of PM_2.5 exposure were also positively associated with preterm birth (OR = 1.17, 95% CI = 1.04–1.30). It is important to protect pregnant women from PM_2.5 exposures, especially during their first trimester of pregnancy even when the ambient PM_2.5 concentration is relatively low. More relevant health policy should be carried out to prevent hazard effect of air pollutants.     

CMC改性的纳米Fe/Cu双金属去除2,4-二氯苯酚的研究

为解决纳米零价金属在水中暴露出的极易聚集与氧化的问题,本研究使用铜作为纳米零价铁(NZVI)的复合金属,制得纳米Fe/Cu双金属,并用羧甲基纤维素钠(CMC)对其包覆改性.使用扫描电子显微镜、X射线衍射以及氮气吸附/脱附等温线对改性前后的双金属进行表征.结果表明,改性之后的材料具有更大的尺寸以及比表面积,且抗氧化性得到显著增强.材料的沉降实验以及对2,4-二氯苯酚(2,4-DCP)降解实验的结果揭示,CMC的包覆比对改性后双金属的分散性与反应活性影响较大.当包覆比为80%时,双金属的分散稳定性最强,释放的活性位点个数最多,表现为最高的反应活性.此时脱氯效率达到90.3%,且脱氯过程和产物发生明显改变.     

不同围岩和埋深条件下高地温隧道围岩稳定性影响研究*

为了研究围岩等级及埋深对高地温隧道围岩稳定性的影响,以红河州建（个）元高速公路尼格隧道为工程背景,采用现场测试、正交试验及数值模拟相结合的方法,探讨围岩等级、埋深及温度对隧道围岩稳定的敏感性。研究结果表明:隧道拱顶沉降量随围岩等级及埋深的升高而增加,而隧道拱顶沉降量随围岩温度的增加呈先减小后增加的趋势,影响隧道拱顶沉降因素主次顺序为围岩等级、埋深及温度。将数值模拟与现场监测结果对比分析,验证数值模拟的可靠性及准确性。研究结果可为类似高地温隧道设计和施工提供参考。