天津市夏季PM10浓度及组成元素垂直分布特征

通过天津市气象局大气边界层观测站高255 m的气象铁塔,获得了10m、40m、120m和220 m 4个高度共80个PM10样品,分析了PM10的日均质量浓度及其元素的垂直分布特征.结果表明,4个高度处PM10质量浓度时序变化基本一致;PM10质量浓度及其组成元素总量随高度增加递减;10 m、40m和120m3个高度处的PM10质量浓度时间序列分布的相关性较好,组分分歧系数较小,而220 m处的PM10质量浓度时间序列分布与其他3个高度处的相关性较差,组分分歧系数较大.样品中元素质量浓度由高到低依次是Si、Al、Ca、Fe、Na、Mg、K、Zn、Ti、Cu、Mn、Pb、Cr、Ni、Co、V、As、Cd和Hg.其中,Si、Al、Na、K质量分数随高度变化不大;Ca、Fe、Mg质量分数随高度增加递减明显;Zn、Cu、Mn、Pb、Cr在10m、40m和120 m3个高度处质量分数接近,而在220m处明显降低;Ti元素在4个高度处的质量浓度接近,质量分数总体上随高度增加递增;Ni、Co、V、As、Cd、Hg质量分数随高度的变化不同,其中与燃煤有密切关系的Hg在120 m处质量分数明显高于其他高度处,而在220m处最低.Al、Fe、Na、K等元素相对富集因子小于或接近1,其质量浓度与PM10质量浓度时序分布的相关性较好,其中Al、Na相关系数随高度增加显著递减;Zn,Cu、Pb、Cr、As、Ni的相对富集因子显著大于1,其质量浓度与PM10质量浓度时序分布的相关性较差,相关系数随高度增加变化不大.     

Model‐Based Nitrogen and Phosphorus (Nutrient) Criteria for Large Temperate Rivers: 2. Criteria Derivation

Nitrogen and phosphorus criteria were developed for 233 km of the Yellowstone River, one of the first cases where a mechanistic model has been used to derive large river numeric nutrient criteria. A water quality model and a companion model which simulates lateral algal biomass across transects were used to simulate effects of increasing nutrients on five variables (dissolved oxygen, total organic carbon, total dissolved gas, pH, and benthic algal biomass in depths ≤1 m). Incremental increases in nutrients were evaluated relative to their impact on predefined thresholds for each variable; the first variable to exceed a threshold set the nutrient criteria. Simulations were made at a low flow, the 14Q5 (lowest average 14 consecutive day flow, July‐September, recurring one in five years), which was derived using benthic algae growth curves and EPA guidance on excursion frequency. An extant climate dataset with an annual recurrence was used, and tributary water quality and flows were coincident with the river's 10 lowest flow years. The river had different sensitivities to nutrients longitudinally, pH being the most sensitive variable in the upstream reach and algal biomass in the lower. Model‐based criteria for the Yellowstone River are as follows: between the Bighorn and Powder river confluences, 55 μg TP/l and 655 μg TN/l; from the Powder River confluence to Montana state line, 95 μg TP/l and 815 μg TN/l. Pros and cons of using steady‐state models to derive river nutrient criteria are discussed.     

单斜相纳米氧化锆基低温SCR催化剂脱硝机制研究

以纳米m-ZrO2为载体,用浸渍法制备出MnOx-CeO2/m-ZrO2催化剂,考察反应温度、活性组分负载量对催化剂NH3-SCR脱硝活性影响,探讨催化剂表面织构特征,分析催化剂脱硝活性机制.结果表明,在低温脱硝温度范围,提高反应温度、增加活性组分负载量,有利于催化剂脱硝效率的增加.110℃时,2.5%MnOx-CeO2/m-ZrO2脱硝效率为55.5%,15%MnOxCeO2/m-ZrO2脱硝效率达93.5%.XRD、BET、XPS、H2-TPR表征结果表明,催化剂表面具有良好的氧化还原能力,表面织构对脱硝反应有利.NH3-TPD测试显示,MnOx-CeO2/m-ZrO2催化剂的脱硝反应机制为:NH3吸附在催化剂表面的Lewis酸性位和Brnsted酸性位上,通过反应生成相应中间产物NH2NO或NH4NO2,中间产物进一步分解最终转变为N2和H2O;催化剂总脱硝反应效率中,在Lewis酸性位上的脱硝反应占比较大.     

植被收割对滨海湿地沉积物中CO_2和N_2O释放的影响

为了揭示冬季滨海湿地植被收割对其沉积物中温室气体释放的影响,以长江入海口典型滨海湿地——崇明东滩为研究对象,观测季节性(冬季)植被收割(分别于收割后第0天、第10天、第30天、第60天采样)与不收割条件下芦苇(Phragmites australis)、米草(Spartina alterniflora)、芦苇-米草交互带和光滩沉积物中CO2与N2O的释放特征.结果表明:1米草和芦苇-米草交互带植被收割并未增加沉积物中CO2的释放(P0.05),但芦苇收割可能会增加N2O的释放(P0.05),说明植被收割对湿地沉积物中CO2和N2O释放的影响与植被类型密切相关.2与芦苇带相比,米草和芦苇-米草交互带沉积物中CO2累积释放量分别高出12%~57%和17%~43%,但芦苇植被覆盖下沉积物中N2O累积释放量分别比二者高出11%~81%和8%~95%.可见,米草和芦苇-米草交互带沉积物碳的呼吸损失明显高于芦苇带,但芦苇植被覆盖下沉积物中N2O逸失量相对较高.34种植被类型下,沉积物中N2O累积释放量为0.1~0.4 mg/kg,CO2累积释放量则高达1 024~2 645 mg/kg.因此,冬季滨海湿地植被收割不会显著增加N2O的温室效应,但选择性收割米草有望减少沉积物碳的呼吸损失.     

Enhanced CO2 adsorptive performance of PEI/SBA-15 adsorbent using phosphate ester based surfactants as additives

In this study,a series of polyetherimide/SBA-15: 2-D hexagonal P6 mm,Santa Barbara USA(PEI/SBA-15) adsorbents modified by phosphoric ester based surfactants(including tri(2-ethylhexyl)phosphate(TEP),bis(2-ethylhexyl) phosphate(BEP) and trimethyl phosphonoacetate(TMPA))were prepared for CO_2 adsorption.Experimental results indicated that the addition of TEP and BEP had positive effects on CO_2 adsorption capacity over PEI/SBA-15.In particular,the CO_2 adsorption amount could be improved by around 20% for 45PEI–5TEP/SBA-15 compared to the additive-free adsorbent.This could be attributed to the decrease of CO_2 diffusion resistance in the PEI bulk network due to the interactions between TEP and loaded PEI molecules,which was further confirmed by adsorption kinetics results.In addition,it was also found that the cyclic performance of the TEP-modified adsorbent was better than the surfactant-free one.This could be due to two main reasons,based on the results of in situ DRIFT and TG-DSC tests.First and more importantly,adsorbed CO_2 species could be desorbed more rapidly over TEP-modified adsorbent during the thermal desorption process.Furthermore,the enhanced thermal stability after TEP addition ensured lower degradation of amine groups during adsorption/desorption cycles.     

Enhanced bio-decolorization of 1-amino-4-bromoanthraquinone-2-sulfonic acid by Sphingomonas xenophaga with nutrient amendment

Bacterial decolorization of anthraquinone dye intermediates is a slow process under aerobic conditions. To speed up the process, in the present study, effects of various nutrients on 1-amino-4-bromoanthraquinone-2-sulfonic acid (ABAS) decolorization by Sphingomonas xenophaga QYY were investigated. The results showed that peptone, yeast extract and casamino acid amendments promoted ABAS bio-decolorization. In particular, the addition of peptone and casamino acids could improve the decolorization activity of strain QYY. Further experiments showed that L-proline had a more significant accelerating effect on ABAS decolorization compared with other amino acids. L-Proline not only supported cell growth, but also significantly increased the decolorization activity of strain QYY. Membrane proteins of strain QYY exhibited ABAS decolorization activities in the presence of L-proline or reduced nicotinamide adenine dinucleotide, while this behavior was not observed in the presence of other amino acids. Moreover, the positive correlation between L-proline concentration and the decolorization activity of membrane proteins was observed, indicating that L-proline plays an important role in ABAS decolorization. The above findings provide us not only a novel insight into bacterial ABAS decolorization, but also an L-proline-supplemented bioaugmentation strategy for enhancing ABAS bio-decolorization.     

Applying a new method for direct collection, volume quantification and determination of N2 emission from water

The emission of N₂ is important to remove excess N from lakes, ponds, and wetlands. To investigate the gas emission from water, Gao et al. (2013) developed a new method using a bubble trap device to collect gas samples from waters. However, the determination accuracy of sampling volume and gas component concentration was still debatable. In this study, the method was optimized for in situ sampling, accurate volume measurement and direct injection to a gas chromatograph for the analysis of N₂ and other gases. By the optimized new method, the recovery rate for N₂ was 100.28% on average; the mean coefficient of determination (R²) was 0.9997; the limit of detection was 0.02%. We further assessed the effects of the new method, bottle full of water, vs. vacuum bag and vacuum vial methods, on variations of N₂ concentration as influenced by sample storage times of 1, 2, 3, 5, and 7 days at constant temperature of 15°C, using indices of averaged relative peak area (%) in comparison with the averaged relative peak area of each method at 0 day. The indices of the bottle full of water method were the lowest (99.5%-108.5%) compared to the indices of vacuum bag and vacuum vial methods (119%-217%). Meanwhile, the gas chromatograph determination of other gas components (O₂, CH₄, and N₂O) was also accurate. The new method was an alternative way to investigate N₂ released from various kinds of aquatic ecosystems.     

Synthesis, crystal structure, photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c= 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^-1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2- and NO₃^-, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography- mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.     

Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO₄ (OMS-2-SO₄) and Mn(CH₃COO)₂ (OMS-2-AC) as precursors. SO₄^2 −-doped OMS-2-AC catalysts with different SO₄^2 − concentrations were prepared next by adding (NH₄)₂SO₄ solution into OMS-2-AC samples to investigate the effect of the anion SO₄^2 − on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO₄ catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO₄^2 − doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO₄^2 − (SO₄/catalyst = 0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH₃-TPD and H₂-TPR techniques. The results showed that the presence of a suitable amount of SO₄^2 − species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO₄ compared to OMS-2-AC is due to the presence of some residual SO₄^2 − species in OMS-2-SO₄ samples.     

Potential application of high pressure carbon dioxide in treated wastewater and water disinfection: Recent overview and further trends

Recently emerging disadvantages in conventional disinfection have heightened the need for finding a new solution. Developments in the use of high pressure carbon dioxide for food preservation and sterilization have led to a renewed interest in its applicability in wastewater treatment and water disinfection. Pressurized CO₂ is one of the most investigated methods of antibacterial treatment and has been used extensively for decades to inhibit pathogens in dried food and liquid products. This study reviews the literature concerning the utility of CO₂ as a disinfecting agent, and the pathogen inactivation mechanism of CO₂ treatment is evaluated based on all available research. In this paper, it will be argued that the successful application and high effectiveness of CO₂ treatment in liquid foods open a potential opportunity for its use in wastewater treatment and water disinfection. The findings from models with different operating conditions (pressure, temperature, microorganism, water content, media …) suggest that most microorganisms are successfully inhibited under CO₂ treatment. It will also be shown that the bacterial deaths under CO₂ treatment can be explained by many different mechanisms. Moreover, the findings in this study can help to address the recently emerging problems in water disinfection, such as disinfection by-products (resulting from chlorination or ozone treatment).