纳米铕吡啶-2,6-二甲酸稀土荧光探针的合成及其性质

合成了纳米铕吡啶-2,6-二甲酸荧光探针,通过测量它的红外光谱、紫外光谱、荧光光谱以及元素分析来研究它的性质.结果表明,铕稀土配合物具有稳定的化学性质和良好的发光性能.荧光光谱表明,铕吡啶-2,6-二甲酸具有良好的荧光性质和生物活性,具有作为荧光探针的性能,可应用于环境分析和时间荧光免疫分析.     

北塘河口沉积物中汞,砷,铬的污染现状和富集特征

由于受上游河流污染的影响,北塘河口沉积物中普遍积累了一定量的汞.本文通过该区域沉积物中汞、砷、铬与有机碳、粘土和铁、铝、锰含量的回归分析,看出这三种元素在沉积物中的富集和分布,主要与水体悬浮物、沉积物中所含有机质,粘土矿物和铁、铝、锰的水合氧化物的含量密切相关.河口淡-咸水界面的水环境中胶体的吸附作用是这些金属离子从溶液转入沉积物的主要途径,水体中的这些金属离子通过悬浮颗粒物和沉积物中有机胶体,无机胶体(粘土矿物和水合氧化物)的吸附,是水体自净的一个极为重要的方面.     

2001—2012年全国水环境质量趋势分析

研究了2001—2012年间全国水环境整体质量及主要流域水环境质量,并进行了趋势分析.分析表明,近年来水环境质量整体呈好转趋势,但形势依然严峻.本文对水质变化的原因进行总结,并提出了水污染严峻形势下急需关注的问题.     

FTIR研究非完全脱乙酰甲壳质对金属离子的吸附机理

以傅立叶交换红外光谱(FTIR)法研究了非完全脱乙酰甲壳质(NCTS)与Cu~ (2+),Ni~(2+),Co~(1+),Zn~(2+),Cd(2+),Hg~(2+),Ag~+,Pb~(2+)等八种金属离子形成的配合物的结构特征,并对各配合物在4000—400cm~(-1)范围内的主要吸收带作了经验归属.研究结果表明,在NCTS的金属离子配合物中,除—NH_2,—OH参予了配位外,羰基((?)C=O)和酰胺基(—CONH—)亦在不同程度上参予了配位;NCTS对Hg~(2+),Ag~+的吸附过程中存在着明显的氧化还原现象,Hg~(2+),Ag~+,分别被还原为Hg_2~(2+)和Ag~0,而NCTS分子中的—CH_2OH有可能被氧化成—COOH.     

无机阴离子对镉、铅解吸特性的影响

土壤中重金属的解吸直接影响重金属在环境中的形态转化和植物有效性.而地表水环境及土壤中的无机阴离子能与重金属离子络合,影响重金属在环境中的迁移和作物的吸收.因此,有关无机阴离子对重金属解吸特性影响的研究,将有利于了解重金属的吸附-解吸机制及其控制措施.文章以我国东北地区草甸棕壤作为研究对象,采用静态解吸实验研究无机阴离子(C1-、SO42-、F-)对土壤中镉、铅的解吸行为的影响.结果表明,土壤中镉、铅的解吸率与无机阴离子类型、浓度密切相关;随着解吸液中无机阴离子(C1-、SO42-、F-)浓度的增大,土壤镉、铅的解吸率随之提高.C1-、SO42-、F-这3种无机阴离子对解吸土壤中镉的影响力顺序是:C1- > SO42- > F-;对解吸土壤中铅的影响力顺序是:SO42- >C1- > F-.     

寒冷地区流域水污染防治问题

我国寒冷地区河流冰封期最长可达180天,其间水体自净功能差,加之城镇污水处理水平低于全国平均水平,工业点源污染负荷沉重,流域水污染问题显得格外突出,水环境压力巨大.因此,有针对性地解决寒冷地区流域水环境问题已经成为协调资源供求、经济发展与环境保护的核心问题.通过分析寒冷地区流域水污染特点及成因,提出了建立流域水污染防治...     

水环境污染源解析研究进展

流域河流水污染问题日益严重,水环境污染源解析的研究与应用对防治水污染具有重要意义.综合国内外水环境污染源解析研究与应用的进展,综述了应用于水环境不同类型污染物源解析的主要理论方法和应用模型;论述了多元统计模型和化学质量平衡法的优缺点、适用范围及应用现状;最后对源解析方法的发展趋势及在水环境中的应用加以展望,指出过去的研究主要是水环境中持久性污染物源解析方法,以后应加强对水环境中非持久性污染源解析的研究,在水环境源解析技术方面,应加强对各类污染源成分谱等基础性研究.     

环境内分泌干扰物与DNA相互作用的光谱研究

采用紫外光谱、荧光光谱和共振光散射光谱,研究了农药类环境内分泌干扰物双酚A以及重金属类内分泌干扰物Cd2 和Pb2 与DNA的相互作用,结果表明,双酚A和重金属离子均能与DNA发生相互作用,双酚A与DNA的作用模式为嵌入模式,金属离子与DNA作用后形成复杂的超分子配合物.     

微波辅助固相顶空-气相色谱法测定人造板材中的苯系物

采用微波辅助固相顶空-气相色谱法测定了人造板材中的苯系物含量,考察了不同微波功率作用下3种苯系物随时间的变化趋势,在优化的条件下测定了3种苯系物的含量.该法检出限为3.6—13.4 ng.g-1板材,RSD为2.7%—9.8%,回收率为86.9%—109.4%,方法简便、快速,适合固体板材中苯系物的直接快速分析.     

抚河流域浮游植物群落结构特征及其水生态状况评价

抚河流域水环境质量呈下降趋势,给沿岸供水甚至鄱阳湖生态安全造成巨大压力,亟需开展全流域生态监测与评价,诊断水生态风险。浮游植物作为水生态系统的初级生产者,能表征水生态环境的变化。针对以往抚河浮游植物群落特征研究主要集中在干流和河口等局部区域,以抚河干流和主要支流为研究对象,于丰(2017年7月)、枯(2017年12月)、平(2018年4月)等3个水文期对抚河流域40个采样点的水环境因子及浮游植物群落结构进行了调查,结合浮游植物的种类组成、优势种、密度、生物多样性等对抚河流域水生态状况进行评价,运用冗余分析方法(Redundancy analysis,RDA),分析抚河流域浮游植物优势种与水环境因子的关系。结果表明：抚河流域共检出浮游植物7门171种,浮游植物细胞密度变化范围为8.33×10⁵-4.43×10⁶ cell·L^-1,优势类群以硅藻、绿藻和蓝藻为主,颗粒沟链藻极狭变种(Aulacoseira granulata var.angustissima (O.Müller)Simonsen)、针杆藻(Synedra E...     

乌鲁木齐市米东区大气降水的化学特征及来源分析

为研究乌鲁木齐市米东区大气降水中的化学组分特征及来源,对2017-2019年降水中主要离子浓度及来源进行了分析.研究结果显示,米东区2017-2019年降水的雨量加权pH年均值为7.95,雨量加权平均电导率年均值为16.15 mS·m-1,雨量加权平均总离子浓度为72.75-95.89 μeq·L-1,年均浓度为81....     

辽宁西南典型城市冬季大气细颗粒物水溶性无机离子污染特征及来源解析

本研究于2018年12月3日-2019年1月1日在辽宁省西南典型城市葫芦岛市和朝阳市分别布设3个城区采样点,在区域传输点龙屯水库布设1个采样点,采集大气细颗粒物PM2.5样品(n=201).使用离子色谱检测样品中的Na+、Mg2+、Ca2+、K+、NH4+、SO42-、F-、Cl-和NO3-的质量浓度.观测期间PM2....     

Zero-valent manganese nanoparticles coupled with different strong oxidants for thallium removal from wastewater

• Nano zero-valent manganese (nZVMn, Mn⁰) is synthesized via borohydrides reduction. • Mn⁰ combined with persulfate/hypochlorite is effective for Tl removal at pH 6-12. • Mn⁰ can activate persulfate to form hydroxyl and sulfate radicals. • Oxidation-induced precipitation and surface complexation contribute to Tl removal. • Combined Mn⁰-oxidants process is promising in the environmental field. Nano zero-valent manganese (nZVMn, Mn⁰) was prepared through a borohydride reduction method and coupled with different oxidants (persulfate (S₂O₈²⁻), hypochlorite (ClO⁻), or hydrogen peroxide (H₂O₂)) to remove thallium (Tl) from wastewater. The surface of Mn⁰ was readily oxidized to form a core-shell composite (MnO_x@Mn⁰), which consists of Mn⁰ as the inner core and MnO_x (MnO, Mn₂O₃, and Mn₃O₄) as the outer layer. When Mn⁰ was added alone, effective Tl(I) removal was achieved at high pH levels (>12). The Mn⁰-H₂O₂ system was only effective in Tl(I) removal at high pH (>12), while the Mn⁰-S₂O₈²⁻ or Mn⁰-ClO⁻ system had excellent Tl(I) removal (>96%) over a broad pH range (4–12). The Mn⁰-S₂O₈²⁻ oxidation system provided the best resistance to interference from an external organic matrix. The isotherm of Tl(I) removal through the Mn⁰-S₂O₈²⁻ system followed the Freundlich model. The Mn⁰ nanomaterials can activate persulfate to produce sulfate radicals and hydroxyl radicals. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that oxidation-induced precipitation, surface adsorption, and electrostatic attraction are the main mechanisms for Tl(I) removal resulting from the combination of Mn⁰ and oxidants. Mn⁰ coupled with S₂O₈²⁻/ClO⁻ is a novel and effective technique for Tl(I) removal, and its application in other fields is worthy of further investigation.     

城市森林大气PM2.5中水溶性无机离子沉降特征

森林被誉为"地球之肺",在防霾治污方面有其独特不可替代的作用,不同树种沉降PM_2.5的功能有很大差别.本文选取代表性城市森林——奥林匹克森林公园为研究对象,设置垂直监测塔观测大气PM_2.5的浓度垂直分布,以考察不同季节城市森林对PM_2.5中各组分的影响.在冬季、春季和夏季各采集PM_2.5样品,分析并计算PM_2.5中Na⁺、NH₄⁺、K⁺、Mg2⁺、Ca2⁺、Cl^-、NO₃^-和SO₄^2-等典型水溶性无机离子的浓度.结果表明,PM_2.5中水溶性无机离子总浓度呈规律性变化特征:冬季((56.90±27.38)μg·m-3)>春季((46.69±12.24)μg·m^-3)>夏季((23.16±8.75)μg·m^-3).其中SO₄^2-和NO₃^-浓度和占PM_2.5主要水溶性无机离子总浓度的50%以上.3个季节中,除冬季外,在春季和夏季,8种离子有明显的垂直方向上的沉降,夏季的沉降速率高于春季,但是春季由于大气颗粒物浓度高,沉降通量高于夏季.NO₃^-和SO₄^2-垂直方向的沉降量在所有可溶性无机离子中最高.植被密度、叶面积指数、气象条件等因素对于PM_2.5的沉降特征有明显影响.     

Performance and mechanism of carbamazepine removal by FeS-S2O82– process: experimental investigation and DFT calculations

● Synergistic removal of carbamazepine (CBZ) was obtained in the FeS-S₂O₈^2– process. ● SO₄^•− and •OH were identified as the main radicals in the FeS-S₂O₈^2– process. ● Heterogeneous oxidation would be dominant first, followed by homogeneous reaction. ● Degradation pathway of CBZ was well elucidated by experiments and DFT calculations. As persulfate (S₂O₈^2–) is being increasingly used as an alternative oxidizing agent, developing low-cost and eco-friendly catalysts for efficient S₂O₈^2– activation is potentially useful for the treatment of wastewater containing refractory organic pollutant. In this study, the degradative features and mechanisms of carbamazepine (CBZ) were systematically investigated in a novel FeS- S₂O₈^2– process under near-neutral conditions. The results exhibited that CBZ can be effectively eliminated by the FeS-S₂O₈^2– process and the optimal conditions were: 250 mg/L FeS, 0.5 mmol/L S₂O₈^2–, and pH = 6.0. The existence of Cl⁻ (1 and 50 mmol/L) has little influence on the CBZ elimination, while both HCO₃⁻ and HPO₄²⁻ (1 and 50 mmol/L) significantly suppressed the CBZ removal in the FeS-S₂O₈^2– process. CBZ could be degraded via a radical mechanism in the FeS-S₂O₈^2– process, the working radical species (i.e., SO₄^•− and •OH) were efficiently formed via the promoted decomposition of S₂O₈^2– by the surface Fe²⁺ on the FeS and the dissolved ferrous ions in solution. Based on the identified oxidized products and Fukui index calculations, a possible degradation pathway of CBZ was speculated. More importantly, a two-stage oxidation mechanism of CBZ elimination was speculated in the FeS-S₂O₈^2– process, the activation of S₂O₈^2– by the surface-active Fe^(II) of FeS dominated in the initial 5 min, while homogeneous oxidation reactions played more essential parts than others in the following reaction stage (5–60 min). Overall, this study demonstrated that the FeS-S₂O₈^2– process is capable of removing CBZ from water efficiently.     

无机离子对左旋葡聚糖光降解的影响

左旋葡聚糖(LG)被广泛作为生物质燃烧的示踪剂.然而,近年来研究表明左旋葡聚糖在大气中不稳定而会发生光降解.此外,对于大气中含量较高的SO₄^2-、NO₃-、NO₂-无机离子对LG光解的影响罕有报到.为此,本文模拟了液相中SO₄^2-、NO₃-、NO₂-对LG光氧化行为的影响.结果表明,Na2SO₄、NaNO₃、NaNO₂条件下LG光解速率常数分别为0.208、0.182、0.165 min^-1,均低于对照组(0.266 min-1),这表明无机离子的存在会减缓LG光降解速率.此外,这3种无机离子对LG光解产物中的低分子脂肪酸分布,甲酸/乙酸(C1/C2)比率均有重要的影响.其中,SO₄^2-存在下产物中戊二酸较多、NO₃-存在下产物中甲酸较多、NO₂-存在下产物中乙酸较多;NO₂-存在下产物中的C1/C2比率小于1与一般二次源中的C1/C2比率不一致,这表明由单一反应引起的C1/C2并不总是大于1.这些结果对于我们深刻理解大气液相中的有机物转化具有重要的参考价值.     

Decoding and quantitative detection of antibiotics by a luminescent mixed-lanthanide-organic framework

● A series of mixed-LOFs and portable LOF-fibers were synthesized. ● LOF-S3 was selected as a luminescent sensor for antibiotics. ● Mixed-LOF was capable of decoding antibiotics by emission intensity ratios. ● Linear relationship between antibiotic concentration and I545nm/I618nm was observed. Due to the potential risk of antibiotics to the environment, the development of inexpensive, simple, and reliable antibiotic detection methods is significant but also faces challenges. In this work, several lanthanide-organic frameworks (LOFs), constructed from lanthanide ions (Eu³⁺ and/or Tb³⁺) and 1,3,5-benzene-tricarboxylic acid (BTC), were synthesized by solvothermal method. LOF-S3 with comparable emission peaks of ⁵D₄ → ⁷F₅ (Tb³⁺, 545 nm) and ⁵D₀ → ⁷F₂ (Eu³⁺, 618 nm) was selected as a luminescent sensor. In this system, the highly efficient energy transferred from the organic linker to lanthanide ions and from Tb³⁺ to Eu³⁺ occurs. LOF-S3 sensor was capable of decoding antibiotics by distinguishable emission intensity ratios. Therefore, a two-dimensional decoded map of antibiotics was established. The linear relationship between antibiotic concentration and emission intensity ratio indicated the quantitative determination of antibiotics was feasible. As a typical analyte, the response mechanism of nalidixic acid (NA) was investigated in detail. The competition of NA and BTC for UV light absorption, as well as the binding propensity of NA and Tb, affected the organic linkers-to-lanthanide ions and Tb-to-Eu energy transfer, resulting in the change of fluorescence intensity ratio. The self-calibrating mixed-LOF sensor overcame the uncontrollable errors of the traditional absolute emission intensity method and generated stable luminescent signals in multiple cycles. Furthermore, the integration of LOF-S3 with polymer fibers enabled the formation of a LOF-polymer fibrous composite with fluorescence detection capability, which is a promising portable sensor for practical applications.     

Oxidation and biotoxicity assessment of microcystin-LR using different AOPs based on UV,O3 and H2O2

MC-LR removal performances under different AOPs were compared systematically. Higher removal efficiency and synergistic effects were obtained by combined process. The acute biotoxicity raised in different degrees after oxidation. Microcystin-LR attracts attention due to its high toxicity, high concentration and high frequency. The removal characteristics of UV/H₂O₂ and O₃/H₂O₂ advanced oxidation processes and their individual process for MC-LR were investigated and compared in this study. Both the removal efficiencies and rates of MC-LR as well as the biotoxicity of degradation products was analyzed. Results showed that the UV/H₂O₂ process and O₃/H₂O₂ were effective methods to remove MC-LR from water, and they two performed better than UV-, O₃-, H₂O₂-alone processes under the same conditions. The effects of UV intensity, H₂O₂ concentration and O₃ concentration on the removal performance were explored. The synergistic effects between UV and H₂O₂, O₃ and H₂O₂ were observed. UV dosage of 1800 mJ·cm⁻² was required to remove 90% of 100 mg·L⁻¹ MC-LR, which amount significantly decreased to 500 mJ·cm⁻² when 1.7 mg·L⁻¹ H₂O₂ was added. 0.25 mg·L⁻¹ O₃, or 0.125 mg·L⁻¹ O₃ with 1.7 mg·L⁻¹ H₂O₂ was needed to reach 90% removal efficiency. Furthermore, the biotoxicity results about these UV/H₂O₂, O₃/H₂O₂ and O₃-alone processes all present rising trends with oxidation degree of MC-LR. Biotoxicity of solution, equivalent to 0.01 mg·L⁻¹ Zn²⁺, raised to 0.05 mg·L⁻¹ Zn²⁺ after UV/H₂O₂ or O₃/H₂O₂ reaction. This phenomenon may be attributed to the aldehydes and ketones with small molecular weight generated during reaction. Advice about the selection of MC-LR removal methods in real cases was provided.     

One-pot hydrothermal fabrication of BiVO4/Fe3O4/rGO composite photocatalyst for the simulated solar light-driven degradation of Rhodamine B

• BiVO₄/Fe₃O₄/rGO has excellent photocatalytic activity under solar light radiation. • It can be easily separated and collected from water in an external magnetic field. • BiVO₄/Fe₃O₄/0.5% rGO exhibited the highest RhB removal efficiency of over 99%. • Hole (h⁺) and superoxide radical (O₂^•−) dominate RhB photo-decomposition process. • The reusability of this composite was confirmed by five successive recycling runs. Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application. In this study, a novel ternary magnetic photocatalyst BiVO₄/Fe₃O₄/reduced graphene oxide (BiVO₄/Fe₃O₄/rGO) was synthesized via a facile hydrothermal strategy. The BiVO₄/Fe₃O₄ with 0.5 wt% of rGO (BiVO₄/Fe₃O₄/0.5% rGO) exhibited superior activity, degrading greater than 99% Rhodamine B (RhB) after 120 min solar light radiation. The surface morphology and chemical composition of BiVO₄/Fe₃O₄/rGO were studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The free radicals scavenging experiments demonstrated that hole (h⁺) and superoxide radical (O₂^•−) were the dominant species for RhB degradation over BiVO₄/Fe₃O₄/rGO under solar light. The reusability of this composite catalyst was also investigated after five successive runs under an external magnetic field. The BiVO₄/Fe₃O₄/rGO composite was easily separated, and the recycled catalyst retained high photocatalytic activity. This study demonstrates that catalyst BiVO₄/Fe₃O₄/rGO possessed high dye removal efficiency in water treatment with excellent recyclability from water after use. The current study provides a possibility for more practical and sustainable photocatalytic process.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.