Investigation of carbonyl compound sources at a rural site in the Yangtze River Delta region of China

Carbonyl compounds are important intermediates in atmospheric photochemistry, but their primary sources are still not understood well. In this work, carbonyls, hydrocarbons, and alkyl nitrates were continuously measured during November 2011 at a rural site in the Yangtze River Delta region of China. Mixing ratios of carbonyls and hydrocarbons showed large fluctuations during the entire measurement. The average level for total measured volatile organic compounds during the pollution episode from 25th to 27th November, 2011 was 91.6 ppb, about 7 times the value for the clean period of 7th–8th, November, 2011. To preliminarily identify toluene sources at this site, the emission ratio of toluene to benzene (T/B) during the pollution episode was determined based on photochemical ages derived from the relationship of alkyl nitrates to their parent alkanes. The calculated T/B was 5.8 ppb/ppb, significantly higher than the values of 0.2–1.7 ppb/ppb for vehicular exhaust and other combustion sources, indicating the dominant influence of industrial emissions on ambient toluene. The contributions of industrial sources to ambient carbonyls were then calculated using a multiple linear regression fit model that used toluene and alkyl nitrates as respective tracers for industrial emission and secondary production. During the pollution episode, 18.5%, 69.0%, and 52.9% of measured formaldehyde, acetaldehyde, and acetone were considered to be attributable to industrial emissions. The emission ratios relative to toluene for formaldehyde, acetaldehyde, and acetone were determined to be 0.10, 0.20 and 0.40 ppb/ppb, respectively. More research on industrial carbonyl emission characteristics is needed to understand carbonyl sources better.     

Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H_2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the Ce O_2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

Removal of formaldehyde over MnxCe1-xO2 catalysts: Thermal catalytic oxidation versus ozone catalytic oxidation

MnxCe1- xO2（x： 0.3–0.9） prepared by Pechini method was used as a catalyst for the thermal catalytic oxidation of formaldehyde（HCHO）. At x = 0.3 and 0.5, most of the manganese was incorporated in the fluorite structure of Ce O2 to form a solid solution. The catalytic activity was best at x = 0.5, at which the temperature of 100% removal rate is the lowest（270°C）. The temperature for 100% removal of HCHO oxidation is reduced by approximately 40°C by loading 5 wt.% Cu Oxinto Mn0.5Ce0.5O2. With ozone catalytic oxidation, HCHO（61 ppm） in gas stream was completely oxidized by adding 506 ppm O3 over Mn0.5Ce0.5O2 catalyst with a GHSV（gas hourly space velocity） of 10,000 hr-1at 25°C. The effect of the molar ratio of O3 to HCHO was also investigated. As O3/HCHO ratio was increased from 3 to 8, the removal efficiency of HCHO was increased from 83.3% to 100%. With O3/HCHO ratio of 8, the mineralization efficiency of HCHO to CO2 was 86.1%. At 25°C, the p-type oxide semiconductor（Mn0.5Ce0.5O2） exhibited an excellent ozone decomposition efficiency of 99.2%,which significantly exceeded that of n-type oxide semiconductors such as Ti O2, which had a low ozone decomposition efficiency（9.81%）. At a GHSV of 10,000 hr-1, [O3]/[HCHO] = 3 and temperature of 25°C, a high HCHO removal efficiency（≥ 81.2%） was maintained throughout the durability test of 80 hr, indicating the long-term stability of the catalyst for HCHO removal.     

挥发性有机污染物(VOCs)治理进展及发展前沿思考

本文介绍了近年国内外在治理可挥发性有机化合物的研究进展,并对吸附与催化技术,低温等离子体-光催化技术等几种先进的处理技术最新发展作了较全面的综述,并对发展前景进行展望。     

南京北郊大气VOCs变化特征及来源解析

利用2011-03-01~2012-02-29南京北郊大气VOCs观测资料,对大气VOCs浓度变化特征和特征物比值差异展开研究,并应用PCA/APCS受体模型对不同季节VOCs来源进行了解析.结果表明,南京大气总VOCs体积混合比为43.52×10-9,其中烷烃占45.1%、烯烃占25.3%、炔烃占7.3%和芳香烃占22.3%.总VOCs体积混合比呈现夏季高,冬季低的季节变化.VOCs组分中烷烃在冬季最高,烯烃夏季最高,芳香烃春季最高,炔烃冬季最高.特征物比值(VOCs/乙炔)和T/B比值反映出观测点受周边工业区影响较大.VOCs源解析表明,主要来源来自工厂生产、机动车排放、燃料燃烧、生产活动挥发、溶剂使用和自然源.虽然有季节变化,但与工业生产活动相关的来源占大气VOCs 45%~63%,其次为机动车来源占34%~50%.     

Characteristics of ozone and ozone precursors (VOCs and NOx) around a petroleum refinery in Beijing, China

A field measurement campaign for ozone and ozone precursors(VOCs and NOx) was conducted in summer 2011 around a petroleum refinery in the Beijing rural region. Three observation sites were arranged, one at southwest of the refinery as the background, and two at northeast of the refinery as the downwind receptors. Monitoring data revealed the presence of serious surface O3 pollution with the characteristics of high average daily mean and maximum concentrations(64.0 and 145.4 ppbV in no-rain days, respectively) and multi-peak diurnal variation. For NOx, the average hourly concentrations of NO2 and NO were in the range of 20.5–46.1 and 1.8–6.4 ppbV, respectively. For VOC measurement, a total of 51 compounds were detected. Normally, TVOCs at the background site was only dozens of ppbC, while TVOCs at the downwind sites reached several hundreds of ppbC. By subtracting the VOC concentrations at background, chemical profiles of VOC emission from the refinery were obtained, mainly including alkanes(60.0% ± 4.3%), alkenes(21.1% ± 5.5%) and aromatics(18.9% ± 3.9%). Moreover, some differences in chemical profiles for the same measurement hours were observed between the downwind sites; the volume ratios of alkanes with low reactivity and those of alkenes with high reactivity respectively showed an increasing trend and a decreasing trend. Finally, based on temporal and spatial variations of VOC mixing ratios, their photochemical degradations and dispersion degradations were estimated to be 0.15–0.27 and 0.42–0.62, respectively, by the photochemical age calculation method, indicating stronger photochemical reactions around the refinery.     

高硫酸盐难降解废水高温厌氧处理中限量曝气的应用及影响

由于硫酸盐还原的影响,普通高温UASB反应器处理亚硫酸盐纸浆厂排出的高硫酸盐难降解废水过程中甲烷菌活性受到了严重抑制.考虑到空气对硫化氢的吹脱和对硫化物的氧化作用可能减轻硫化物对甲烷菌的抑制,本研究在厌氧反应器中引入限量曝气措施.试验结果表明,反应器的运行稳定性和处理能力均得到大幅提高.在有机负荷提高到原来2倍的情况下,曝气后COD去除率仍有提高,从40%～50%提高到60%～70%.试验证明部分甲烷菌可以耐氧,而某些种类的水解酸化细菌则对不完全厌氧环境比较敏感.     

Determination and distribution characteristics of degradation products of nonylphenol polyethoxylates in the rivers of Taiwan

Concentrations of degradation products of nonylphenol polyethoxylates (NPEOs) were analyzed in river water samples in order to determine the distribution characteristic of these alkylphenolic compounds in 18 major rivers of Taiwan. The degradation products of NPEOs were detected in all river samples, with the dicarboxylates alkylphenolic degradation products (CAPEC) being detected most frequently and at the highest concentrations. Concentrations of NP and NP1EO in rivers ranged from n.d. to 5.1 μg l⁻¹ and n.d. to 0.5 μg l⁻¹, respectively. The total concentrations of shortened carboxylates (i.e., NP1EC + NP2EC + NP3EC) and dicarboxylates alkylphenolic degradation products (CAP1EC + CAP2EC) ranged from n.d. to 63.6 μg l⁻¹ and n.d. to 94.6 μg l⁻¹, respectively. Concentrations of NP2EC, NP3EC and all CAPEC residues were determined semi-quantitatively by comparing with the internal standard. Significantly higher concentrations of CAPEC residues were detected in the river waters as compared to those of NP, NP1EO and NPEC degradation products and the average proportions of these compounds in the samples of the rivers were as follows: NP + NP1EO was 5 ± 2.5%, total NPEC was 25 ± 12%, and total CAPEC was 70 ± 12%. The high concentration ratios of CAPEC/NPEC illustrate that aerobic biodegradation plays a main route in the fate of NPEO in the rivers of Taiwan.     

Isolation and Identification of Antialgal Compounds from the Leaves of Vallisneria spiralis L. by Activity-Guided Fractionation (5 pp)

Background, Aims and Scope

Vallisneria spiralis Linn., a common, submerged macrophyte, is widely available in quiet waters of lakes, ponds, marshes and streams in Southeast Asia. V. spiralis plays a significant role not only in decreasing eutrophication of water body for its productivity, but also in inhibiting the growth of blue-green algae? The aim of the paper involves the isolation and identification of allelochemicals from extracts of V. spiralis by activity-guided fractionation and column chromatography.

Methods

Leaves of V. spiralis was washed free of debris, air-dried and refluxed in 95% EtOH. The extract was isolated using column chromatography and fractionation with antialgal activity. Potential allelochemicals were analyzed by high-resolution gas chromatography-mass spectrometry (HRGC-MS).

Results

Two fractions with strong antialgal activity were isolated using column chromatography and activity-guided fractionation from the extract of V. spiralis. 2-Ethyl-3-methylmaleimide, dihydroactinidiolide and 4-oxo-β-Ionone were identified in the first fraction, and 3-hydroxy-5,6-epoxy-β-ionone, loliolide, 6-hydroxy-3-oxo-α-ionone and an unknown compound in the second fraction. They had strong inhibitory effects on Microcystis aeruginosa Kütz.

Discussion

2-Ethyl-3-methylmaleimide is a byproduct of photooxidation of chlorophyll, and five other compounds identified were derivatives of β-carotene. HRGC-MS and derivatization technology were used to identify and confirm their molecular structures. The formula of the unknown compound was C16H19NO4. Metabolites of plant pigments had strong inhibitory activities on growth of algae.

Conclusions

Six compounds had been identified in V. spiralis, among them, 2-ethyl-3-methylmaleimide was the main allelochemical, and derivatives of ionone were also potential allelochemicals.

Recommendations and Perspective

. The results of our research could help us to study further mechanisms of inhibitory effect on algae and develop new potential antialgal substances.     

Assessment of the risk of excess sulfur input into terrestrial ecosystems of the Kola Peninsula

The tolerance of terrestrial ecosystems of the Kola Peninsula to atmospheric deposition of acid-forming sulfur compounds and the risk of their excess input into these ecosystems have been assessed on the basis of the critical load concept. The most sensitive ecosystems (critical sulfur load <400 equiv/ha per year) occupy 58% of the total area of the peninsula. These are mainly pine, spruce, and birch forests (including open and crooked birch forests) growing on podzols formed on sandy boulder-pebble glacial deposits. The zones of ecological risk cover the northwestern and central parts of the peninsula near the Pechenganikel and Severonikel combined works (20% of the total area).