柴油机尾气中微粒粒径分布特征的实验研究

柴油机尾气中的微粒粒径大小分布范围广泛,不同直径的微粒所占的比例以及对环境和人身健康造成的危害各不相同,因此对微粒粒径特征进行研究更具有实际意义。本研究分别采用滤膜称重法和光散射法对厦工XG951Ⅲ装载机配置的国Ⅲ柴油发动机怠速工况下的尾气进行测试,研究了微粒的质量浓度分布、数量浓度分布以及质量浓度与数量浓度分布的关系。研究结果表明,从微粒质量上看,可吸入微粒(PM10)占微粒总量(TSP)的74.0%,可入肺微粒(PM2.5)占可吸入微粒的48.1%;2.5μm以下粒径范围内的微粒质量浓度是2.5~10μm粒径范围内微粒质量浓度的将近3倍,是10~100μm粒径范围内微粒质量浓度的52倍;2.5~10μm粒径范围的微粒质量浓度是10~100μm粒径范围内微粒质量浓度的18倍。数量上,在不同的数量级上,微粒数量浓度随粒径变化差距很明显,尤其是1μm以下的微粒较多。另外,质量浓度的粒径分布滞后于数量浓度。因此PM2.5排放标准中应考虑以个数浓度代替质量浓度为标准。     

Fe3O4纳米磁性微粒对全氟辛烷磺酸盐的吸附

采用共沉淀法合成Fe3O4纳米磁性颗粒,用透射电子显微镜(TEM)、X射线衍射仪(XRD)以及振动样品磁强计(VSM)对Fe3O4纳米磁性颗粒的粒径、形貌和磁性进行表征并研究Fe3O4纳米磁性微粒对全氟辛磺酸盐的吸附。结果表明:在PFOS初始浓度4 mg/L,pH为3,反应时间24 h,Fe3O4纳米磁性微粒投加量1.25 g/L,对全氟辛磺酸盐去除率达到90%。Fe3O4纳米磁性微粒对PFOS的吸附符合Freundlich吸附方程。     

巯基酯化壳聚糖的合成及对Cd~(2+)的去除性能研究

采用化学方法,研究了以巯基甲壳质制备巯基酯化壳聚糖的最佳合成方案。研究表明,巯基甲壳质的脱乙酰条件(包括时间、温度、氢氧化钠浓度)影响其产物巯基酯化壳聚糖对重金属镉离子的吸附效果。当脱乙酰时间为2 h,温度为160℃,氢氧化钠浓度为20%时,20 mg的合成产物对30 mL Cd2+浓度为20 mg/L水样的去除率最高,达到85.46%,其对镉离子的吸附量达到28.5 mg/g。通过对产物进行红外分析发现,巯基甲壳质中出现脂基特征峰值,脱乙酰后脂基并没有消失,证明最后的产物为巯基酯化壳聚糖。     

表面活性剂底喷填料塔的氯化铵微粒脱除增效作用

为高效去除微细颗粒物和减少水雾排放,设计了一种底喷式填料塔,利用表面活性剂能降低水的表面张力的原理,对比分析饮用水、SDBS、AEO-9、A-7对粒径小于1μm的氯化铵微粒的净化效果。结果表明,当底喷填料塔入口氯化铵微粒质量浓度为124.9～194.3 mg·m~(-3)时,饮用水洗涤液的微粒脱除效率仅在40%左右,出口氯化铵微粒质量浓度70 mg·m~(-3);当采用SDBS和AEO-9表面活性剂洗涤液后,微粒脱除效率大幅提高。AEO-9的提效作用较明显,当AEO-9浓度增至0.004%时,脱除效率达到74.8%,氯化铵微粒出口浓度为26.5 mg·m~(-3);当采用浓度为0.3%的A-7洗涤液时,脱除效率为89%,此时氯化铵微粒出口浓度仅为15 mg·m~(-3)。通过分析可知,表面活性剂洗涤液对微细颗粒物的脱除有提效作用。     

Fe3O4纳米磁性微粒对全氟辛烷磺酸盐的吸附

采用共沉淀法合成Fe3O4纳米磁性颗粒,用透射电子显微镜（TEM）、X射线衍射仪（XRD）以及振动样品磁强计（VSM）对Fe3O4纳米磁性颗粒的粒径、形貌和磁性进行表征并研究Fe3O4纳米磁性微粒对全氟辛磺酸盐的吸附。结果表明：在PFOS初始浓度4 mg/L,pH为3,反应时间24 h,Fe3O4纳米磁性微粒投加量1.25 g/L,对全氟辛磺酸盐去除率达到90%。Fe3O4纳米磁性微粒对PFOS的吸附符合Freundlich吸附方程。     

巯基酯化壳聚糖的合成及对 Cd2 +的去除性能研究简

采用化学方法，研究了以巯基甲壳质制备巯基酯化壳聚糖的最佳合成方案。研究表明，巯基甲壳质的脱乙酰条件（包括时间、温度、氢氧化钠浓度）影响其产物巯基酯化壳聚糖对重金属镉离子的吸附效果。当脱乙酰时间为2 h，温度为160℃，氢氧化钠浓度为20%时，20 mg的合成产物对30 mL Cd²⁺浓度为20 mg/L水样的去除率最高，达到85.46%，其对镉离子的吸附量达到28.5 mg/g。通过对产物进行红外分析发现，巯基甲壳质中出现脂基特征峰值，脱乙酰后脂基并没有消失，证明最后的产物为巯基酯化壳聚糖。     

壳聚糖/纳米CdS复合颗粒可见光光催化降解猩红B动力学研究

采用仿生矿化法制备了壳聚糖/纳米CdS复合颗粒光催化剂,并用于可见光光催化降解猩红B染料模拟废水,研究了猩红B初始浓度、pH、催化剂投加量和催化剂重复使用次数等因素对猩红B光催化降解的影响.X射线衍射(XRD)分析表明,壳聚糖能有效负载CdS纳米微晶.采用Langmuir-Hinshelwood模型描述壳聚糖/纳米CdS复合颗粒可见光光催化降解猩红B反应动力学行为,在猩红B初始质量浓度较低(≤20 mg/L)时,光催化降解过程符合假一级动力学方程.降低猩红B初始浓度和溶液pH都可显著增大光催化降解速率常数;催化剂投加量小于0.7 g/L时,光催化降解速率随其增加而增大,但催化剂投加量过大会使光催化降解速率减小;催化剂重复使用第5次时,猩红B光催化降解速率常数仍为第1次使用时的63.4%.     

Fe3O4/SDS磁性纳米颗粒吸附水体中的Cd2+和Zn2+

一种新型纳米固相萃取吸附剂,由阴离子表面活性剂十二烷基磺酸钠(SDS)包裹在Fe3O4磁性纳米颗粒表面形成,用于吸附水溶液中的重金属离子。研究了吸附过程的主要影响因素(如SDS浓度、溶液pH等)以及解吸过程的最佳条件,并对其机理进行了初步的探讨。研究结果表明,共沉淀法制备的Fe3O4颗粒粒径分布均匀,平均粒径约为54 nm;SDS浓度为300 mg/L时,Fe3O4/SDS磁性纳米颗粒吸附Cd2+和Zn2+的能力最强;在一定浓度范围内,Fe3O4/SDS体系对Cd2+和Zn2+的吸附平衡数据符合Langmuir吸附等温方程,饱和吸附量分别为22.42 mg/g和13.95 mg/g。最终结果表明,Fe3O4/SDS磁性纳米颗粒具有较强磁分离能力和较好的吸附效果。     

天然黄铁矿对水溶液中硒酸根的吸附性能研究

进行了不同黄铁矿粒径、初始硒浓度、温度和pH条件下黄铁矿吸附Se(Ⅳ)(SeO23-)的实验研究。在12h的实验时间内,微米级的黄铁矿对初始硒质量浓度为7.896、19.740、39.480mg/L的Se(Ⅳ)的去除率分别为18%、11%和6%,而纳米级的黄铁矿对同浓度Se(Ⅳ)的去除率均达到91%以上。室温下,纳米级黄铁矿对Se(Ⅳ)饱和吸附量为3.89mg/g。在pH为2.2~11.5时,黄铁矿对Se(Ⅳ)的吸附率均超过92%,纳米级黄铁矿吸附Se(Ⅳ)的过程符合准二级动力学方程,反应活化能为26.003kJ/mol,实验数据与Langmuir吸附等温模型拟合较好。     

水溶性巯基壳聚糖对污染土壤吸附态汞的解吸作用研究

用两种巯基化试剂半胱氨酸(Cys)和硫代乙醇酸(Thi)与壳聚糖(CTS)反应,制备了两种水溶性巯基壳聚糖,即Cys-CTS和Thi-CTS,对比研究了这两种巯基壳聚糖与CTS对被染毒土壤中吸附态汞的提取能力.结果表明,Thi-CTS在pH=3、质量浓度为0.5g/L、用量为20 mL的条件下.对汞的提取率为59.44%,相同条件下CTS和cys-CTS对汞的最高提取率只有31.81%和10.15%.     

Impact of dilution on the transport of poly(acrylic acid) supported magnetite nanoparticles in porous media

This paper investigates the impact of dilution on the mobility of magnetite nanoparticles surface coated with poly(acrylic acid) (PAA). Transport experiments were conducted in a water-saturated sand-packed column for input nanoparticle solutions with total Fe concentrations ranging from 100 to 600mg/L. Particle size analysis of the synthesized nanoparticle solutions showed that PAA provides good size stability for Fe concentrations as low as about 1mg/L. Time-moment analysis of the nanoparticle breakthrough curves, on the other hand, revealed that nanoparticle mass recovery from the column decreased consistently with dilution, with greater attenuation, sharper fronts and longer tails compared to that of the tracer. Particle size analysis of the eluted solutions shows that the nanoparticle size is negatively correlated with nanoparticle concentration. Modeling results suggest that the decrease in nanoparticle mobility with input concentration can be represented using a kinetic time-dependent deposition term with finite deposition capacity and a kinetic detachment term. For field applications, the increase in particle size and detachment resulting from dilution means reduced transport efficiency of nanoparticles and reaction potential with travel distance.     

Effect of particle size of titanium dioxide nanoparticle aggregates on the degradation of one azo dye

Introduction

Titanium dioxide (TiO₂) nanoparticle powders have been extensively studied to quickly photodegrade some organic pollutants; however, the effect of the particle size of TiO₂ nanoparticle aggregates on degradation remains unclear because microscale aggregates form once the nanoparticle powders enter into water.

Methods

The degradation of azo dye by different particle sizes of TiO₂ nanoparticle aggregates controlled by NaCl concentrations was investigated to evaluate the particle size effect. Removal reactions of reactive black 5 (RB5) with TiO₂ nanoparticles followed pseudo-first-order kinetics.

Results

The increase of TiO₂ dosage from 40 to 70?mg/L enhanced the degradation. At doses around 100?mg/L TiO₂, degradation rates decreased which could be the result of poor UV light transmittance at high-particle concentrations. At average particle sizes of TiO₂ nanopowders less than around 500?nm, the degradation rates increased with decreasing particle size. As the average particle size exceeded 500?nm, the degradation rates were not significantly changed.

Conclusions

For the complete degradation experiments, the mineralization rates of total organic carbon disappearance are generally following the RB5 decolorization kinetic trend. These findings can facilitate the application of TiO₂ nanoparticles to the design of photodegradation treatments for wastewater.     

Impact of molybdenum nanoparticles on survival,activity of enzymes,and chemical elements in <Emphasis Type="Italic">Eisenia fetida</Emphasis> using test on artificial substrata

The influence of molybdenum oxide nanoparticles (MoO₃) on the growth and survival of Eisenia fetida was established. The activity of antioxidant enzymes and changes in concentration of molybdenum in the body of E. fetida were determined. The degree of bacterial bioluminescence inhibition in extracts of substrates and worm was studied using luminescent strain Escherichia coli K12 TG1. The enzymatic activity of substrates before and after exposure with nanoparticles and worms was assessed. Nanoparticles have concentrations of 10, 40, and 500 mg/kg of dry matter, and substrata are made of artificial soil (substrate A) and microcrystalline cellulose (substrate B). Spherical nanoparticles MoO₃, yellow in color, with size 92?±?0.3 nm, Z-potential 42?±?0.52 mV, molybdenum content 99.8 mass/%, and specific area 12 m²/g were used in the study. A significant decrease by 23.3 % in weight was registered (for MoO₃ NPs at 500 mg/kg) on substrate A (p?≤?0.05). On substrate B, the maximum decrease in weight by 20.5, 33.3, and 16.9 % (p?≤?0.05) was registered at a dose of 10, 40, and 500 mg/kg, respectively; mortality was from 6.6 to 73 %. After the assessment of bacterial bioluminescence inhibition in substrates A and B (extracts) and before worms were put, the toxicity of substrates was established at doses of 40 and 500 mg/kg, expressed in inhibitory concentration (IC) 30 and IC 50 values. Comparatively, on days 7 and 14, after exposure in the presence of E. fetida, no inhibition of bioluminescence was registered in extracts of substrates A and B, indicating the reduction in toxicity of substrates. The initial content of molybdenum in E. fetida was 0.9?±?0.018 mg/kg of dry matter. The degree of molybdenum accumulation in worm tissue was dependent on the dose and substrate quality. In particular, 2–7 mg/kg of molybdenum accumulated from substrate A, while up to 15 kg/kg of molybdenum accumulated from substrate B (day 7). Molybdenum concentration decreased by 64.8 and 57.4 % at doses 40 and 500 mg/kg, respectively, on day 14. The reaction of antioxidant enzymes was shown in an insignificant increase of glutathione reductase (GSR) and catalase (CAT) at concentrations of 10 and 40 mg/kg in substrate A, followed by the subsequent reduction of their activity at the dose of 500 mg/kg MoO₃. The activity of GSR in substrate B against the presence of MoO₃ nanoparticles decreased, with significant difference of 33.5 % (p?≤?0.05) at the dose of 500 mg/kg compared with untreated soil. In experiments with substrate A, an increase of catalase activity was registered for the control sample. The presence of MoO₃ nanoparticles at the concentration of 10 mg/kg in the environment promoted enzymatic activity on days 7 and 14, respectively. A further increase of nanoparticle concentration resulted in the decrease of catalase activity with a minimum value at the concentration of MoO₃ of 500 mg/kg. In the experiment with substrate B at the concentration of MoO₃ nanoparticles of 40 mg/kg, enzymatic activity increases on day 7 of exposure. However, the stimulating effect of nanoparticles stops by day 14 of the experiment and further catalase activity is dose dependent with the smallest value in the experiment with MoO₃ having the concentration of 500 mg/kg.     

纳米氧化铈对汽油发动机尾气污染物排放的影响

通过非水微乳液法制备了纳米氧化铈，并将之添加到90^#汽油中，研究了纳米氧化铈对汽油动力性能、尾气污染物CO、HC、PM、NOx排放的影响。结果表明：非水微乳液法制备的纳米氧化铈粒径在30～50nm之间，粒径分布较窄；添加浓度为100mg／L时，不会对汽油的动力性能产生明显影响，但可以明显降低90。汽油尾气中的CO、HC、PM、NOx排放。其中，800r／min的正常怠速下可以降低CO排放19．39％、HE排放19．92％、NOx排放51．19％、PM排放25％；在2000r／min的高怠速下可降低CO排放16．17％、NOx排放46．92％、PM排放16．67％。     

Ecotoxic Effect of Photocatalytic Active Nanoparticles (TiO2) on Algae and Daphnids (8 pp)

Background, Aim and Scope Due to their large potential for manifold applications, the use of nanoparticles is of increasing importance. As large amounts of nanoparticles may reach the environment voluntarily or by accident, attention should be paid on the potential impacts on the environment. First studies on potential environmental effects of photocatalytic TiO2 nanoparticles have been performed on the basis of widely accepted, standardized test systems which originally had been developed for the characterization of chemicals. The methods were adapted to the special requirements of testing photocatalytic nanoparticles. Materials and Methods: Suspensions of two different nanoparticles were illuminated to induce their photocatalytic activity. For testing, the growth inhibition test with the green alga Desmodesmus subspicatus and the immobilization test with the daphnid Daphnia magna were selected and performed following the relevant guidelines (algae: ISO 8692, OECD 201, DIN 38412-33; daphnids: ISO 6341, OECD 202, DIN 38412-30). The guidelines were adapted to meet the special requirements for testing photocatalytic nanoparticles. Results: The results indicate that it is principally possible to determine the ecotoxicity of nanoparticles. It was shown that nanoparticles may have ecotoxicological effects which depend on the nature of the particles. Both products tested differ in their toxicity. Product 1 shows a clear concentration-effect curve in the test with algae (EC50: 44 mg/L). It could be proven that the observed toxicity was not caused by accompanying contaminants, since the toxic effect was comparable for the cleaned and the commercially available product. For product 2, no toxic effects were determined (maximum concentration: 50 mg/L). In the tests with daphnids, toxicity was observed for both products, although the concentration effect-curves were less pronounced. The two products differed in their toxicity; moreover, there was a difference in the toxicity of illuminated and non-illuminated products. Discussion: Both products differ in size and crystalline form, so that these parameters are assumed to contribute to the different toxicities. The concentration-effect curves for daphnids, which are less-pronounced than the curves obtained for algae, may be due to the different test organisms and/or the differing test designs. The increased toxicity of pre-illuminated particles in the tests with daphnids demonstrates that the photocatalytic activity of nanoparticles lasts for a period of time. Conclusions: The following conclusions can be drawn from the test results: (I) It is principally possible to determine the ecotoxicity of (photocatalytic) nanoparticles. Therefore, they can be assessed using methods comparable to the procedures applied for assessing soluble chemicals. - (II) Nanoparticles may exert ecotoxicological effects, which depend on the specific nanoparticle. - (III) Comparable to traditional chemicals, the ecotoxicity depends on the test organisms and their physiology. - (IV) The photocatalytic activity of nanoparticles lasts for a relevant period of time. Therefore, pre-illumination may be sufficient to detect a photocatalytic activity even by using test organisms which are not suitable for application in the pre-illumination-phase. Recommendations and Perspectives: First results are presented which indicate that the topic 'ecotoxicity and environmental effects of nanoparticles' should not be neglected. In testing photocatalytic nanoparticles, there are still many topics that need clarification or improvement, such as the cause for an observed toxicity, the improvement of the test design, the elaboration of a test battery and an assessment strategy. On the basis of optimized test systems, it will be possible to test nanoparticles systematically. If a potential risk by specific photocatalytic particles is known, a risk-benefit analysis can be performed and, if required, risk reducing measures can be taken.     

Assessment of transport of two polyelectrolyte-stabilized zero-valent iron nanoparticles in porous media

This study investigated the breakthrough patterns of carboxymethyl cellulose- and polyacrylic acid-stabilized zero-valent iron (Fe(0)) nanoparticles (NZVI) from packed sand columns under a range of pore water velocities of 0.02, 0.2 and 1 cm min(-1) and NZVI influent concentrations of 0.1, 0.5 and 3 g L(-1). The NZVI effluent relative concentrations of both types of particles decreased with slower flow velocities and increasing particle concentrations. PAA-NZVI exhibited slower elution from the columns than CMC-NZVI under identical experimental conditions, and this is attributed to more rapid aggregation kinetics of PAA-NZVI. The elution patterns of PAA-NZVI showed a stronger trend of gradually increasing effluent concentrations with flushing of additional pore volumes, especially at low flushing velocities and higher influent particle concentrations and this phenomenon too can be attributed to increasing aggregate sizes with time which caused decreases in the values of the single collector efficiency and thus the deposition rate constant. A 7 nm increase in CMC-NZVI aggregate size over 60 min was observed using nanoparticle tracking analysis. The reduction in colloidal stability due to aggregation of CMC- and PAA-NZVI was verified using sedimentation tests, and it was found that PAA-NZVI were less stable than CMC-NZVI. There were also notable inherent differences in the two NZVI particles. The CMC-NZVI were monodisperse with a mean diameter of 5.7 ± 0.9 nm, whereas PAA-NZVI had a bimodal particle size distribution with a small sub-population of particles with mean size of 30 ± 21 nm and a more abundant population of 4.6 ± 0.8 nm diameter particles. Furthermore, PAA-NZVI had a lower surface potential. These characteristics are also responsible for the different elution patterns CMC- and PAA-NZVI.     

In situ immobilization of Cu(II) in soils using a new class of iron phosphate nanoparticles

This study tested the feasibility of using a new class of iron phosphate (vivianite) nanoparticles synthesized using sodium carboxymethyl cellulose (NaCMC) as a stabilizer for in situ immobilization of Cu(II) in soils. Transmission electron microscopy measurements demonstrated that the particle size was about 8.4+/-2.9 nm. Batch tests showed that nano-sized vivianite particles can effectively reduce the leachability and in vitro bioaccessibility of Cu(II) in three representative soils (calcareous, neutral, and acidic) at the low doses of 0.61 and 3.01 mg PO(4) g(-1) soil. The Cu leachability was evaluated by the toxicity characteristic leaching procedure and in vitro bioaccessibility was evaluated by the physiological based extraction test. In the case of soil amendment with nanoparticles in 3.01 mg PO(4) g(-1) soil, Cu leachability reduced 63-87% and Cu concentrations in TCLP extract decreased from 1.74-13.33 mg l(-1) to 0.23-2.55 mg l(-1) after those soils were amended for 56 d. Meanwhile, the bioaccessibility of Cu was reduced by 54-69%. Sequential extraction procedures showed the significant decrease of water soluble/exchangeable Cu(II) and carbonate bound fractions and concomitant increase of Cu residual fraction after the soils were amended with the nanoparticles, suggesting that the formation of copper phosphate minerals through precipitation and adsorption was probably responsible for the decrease of Cu availability in soils. Visual MINTEQ modeling further revealed that Cu(3)(PO(4))(2) and Cu(5)(PO(4))(3)OH were formed in the vivianite-solid Cu(II) system, resulting in the decreased solubility of the Cu(II) in the acidic pH range.     

Fe_3O_4/SDS磁性纳米颗粒吸附水体中的Cd~（2＋）和Zn~（2＋）

一种新型纳米固相萃取吸附剂,由阴离子表面活性剂十二烷基磺酸钠（SDS）包裹在Fe3O4磁性纳米颗粒表面形成,用于吸附水溶液中的重金属离子。研究了吸附过程的主要影响因素（如SDS浓度、溶液pH等）以及解吸过程的最佳条件,并对其机理进行了初步的探讨。研究结果表明,共沉淀法制备的Fe3O4颗粒粒径分布均匀,平均粒径约为54 nm;SDS浓度为300 mg/L时,Fe3O4/SDS磁性纳米颗粒吸附Cd2＋和Zn2＋的能力最强;在一定浓度范围内,Fe3O4/SDS体系对Cd2＋和Zn2＋的吸附平衡数据符合Langmuir吸附等温方程,饱和吸附量分别为22.42 mg/g和13.95 mg/g。最终结果表明,Fe3O4/SDS磁性纳米颗粒具有较强磁分离能力和较好的吸附效果。     

A mobile pollutant measurement laboratory—measuring gas phase and aerosol ambient concentrations with high spatial and temporal resolution

A mobile pollutant measurement laboratory was designed and built at the Paul Scherrer Institute (Switzerland) for the measurement of on-road ambient concentrations of a large set of trace gases and aerosol parameters with high time resolution (<15 s for most instruments), along with geographical and meteorological information. This approach allowed for pollutant level measurements both near traffic (e.g. in urban areas or on freeways/main roads) and at rural locations far away from traffic, within short periods of time and at different times of day and year. Such measurements were performed on a regular base during the project year of gas phase and aerosol measurements (YOGAM). This paper presents data measured in the Zürich (Switzerland) area on a late autumn day (6 November) in 2001. The local urban particle background easily reached 50 000 cm⁻³, with additional peak particle number concentrations of up to 400 000 cm⁻³. The regional background of the total particle number concentration was not found to significantly correlate with the distance to traffic and anthropogenic emissions of carbon monoxide and nitrogen oxides. On the other hand, this correlation was significant for the number concentration of particles in the size range 50–150 nm, indicating that the particle number concentration in this size range is a better traffic indicator than the total number concentration. Particle number size distribution measurements showed that daytime urban ambient air is dominated by high number concentrations of ultrafine particles (nanoparticles) with diameters <50 nm, which are immediately formed by traffic exhaust and thus belong to the primary emissions. However, significant variation of the nanoparticle mode was also observed in number size distributions measured in rural areas both at daytime and nighttime, suggesting that nanoparticles are not exclusively formed by primary traffic emissions. While urban daytime total number concentrations were increased by a factor of 10 compared to the nighttime background, corresponding factors for total surface area and total volume concentrations were 2 and 1.5, respectively.