Summer air quality over an artificial lake

In the summer of 1998, the air quality (indicators: CO, NO, NO₂, O₃) above the water surface of the Lake Balderey (Essen, Ruhr area, North Rhine-Westphalia, Germany), an artificial lake used for recreation purposes, was measured using the Fourier transform infrared spectroscopy (FTIR) and differential optical absorption spectroscopy (DOAS) remote measurement methods. The lake, with an area of 3 km² was created by damming the Ruhr and is surrounded by higher ground. In calm, bright weather conditions, this location results in a low-exchange situation (formation of temperature inversions, cold air dynamics) with a sustained impact on pollutant concentrations over the lake. The results of trace substance measurements (1/2 h mean values) were compared with values from comparison stations (suburban, high traffic and forest) located outside the area of the lake. In general, it was found that mean CO and NO concentrations over the lake were very low (0.3 ppm and 7.5 ppb, respectively). NO₂ values (15 ppb) were some 3.5 times higher than those recorded at the forest station and O₃ values, at 27 ppb, almost reached the same level as at the forest station (30 ppb). Mass flow densities as a function of wind direction, diurnal courses, differences between weekdays and weekends and comparisons with air quality standards are presented for the lake station.     

The Danish eulerian hemispheric model — a three-dimensional air pollution model used for the arctic

A three-dimensional Eulerian hemispheric air pollution model, the Danish Eulerian Hemispheric Model (DEHM), is in development at the National Environmental Research Institute (NERI). The model has been used to study long-range transport of air pollution in the Northern Hemisphere. The present version of the model includes long-range transport of sulphur dioxide (SO₂) and particulate sulphate (SC₄²⁻. The chemistry in the model is described by a simple linear oxidation of SO₂ to SO₄²⁻, and the wet deposition of SO₂ and SO₄⁻ is estimated based on the amount of precipitation, which is calculated from the contents of liquid cloud water (see Christensen, Air Pollution Modelling and its Applicatioons, Vol. X, pp. 119–127, Vol. XI, pp. 249–256, Plenum press, New York; 1995, Ph.D. thesis, National Environmental Research Institute, Denmark). The model has been used to study the air pollution in the Arctic. Results from yr simulation with an analysis of the results is presented: the model results are verified by comparisons, to measurements not only from the Arctic region but also from Europe and Canada. Some examples of episodes in the Arctic including analysis of the meteorological conditions during the episodes are presented. Finally, the model has been used to estimate the contribution from the different source regions on the northern hemisphere to the Arctic sulphur pollution.     

Relationship between ammonia stomatal compensation point and nitrogen metabolism in arable crops: current status of knowledge and potential modelling approaches

The ammonia stomatal compensation point of plants is determined by leaf temperature, ammonium concentration ([NH4+]apo) and pH of the apoplastic solution. The later two depend on the adjacent cells metabolism and on leaf inputs and outputs through the xylem and phloem. Until now only empirical models have been designed to model the ammonia stomatal compensation point, except the model of Riedo et al. (2002. Coupling soil-plant-atmosphere exchange of ammonia with ecosystem functioning in grasslands. Ecological Modelling 158, 83-110), which represents the exchanges between the plant's nitrogen pools. The first step to model the ammonia stomatal compensation point is to adequately model [NH4+]apo. This [NH4+]apo has been studied experimentally, but there are currently no process-based quantitative models describing its relation to plant metabolism and environmental conditions. This study summarizes the processes involved in determining the ammonia stomatal compensation point at the leaf scale and qualitatively evaluates the ability of existing whole plant N and C models to include a model for [NH4+]apo.     

赋磁硅气凝胶的制备、表征和吸附异狄氏剂特性

以工业水玻璃为硅源,采用六甲基二硅胺烷(HMDZ)作为改性剂,掺杂纳米级Fe3O4,通过溶胶-凝胶、常压干燥技术,制备得到赋磁硅气凝胶吸附材料(MSA)。采用红外光谱(FTIR)、扫描电镜(SEM)、比表面分析(BET)及振动样品磁强计(VSM)等方法对其结构进行了表征,并对其吸附性能进行研究。结果表明,制得的赋磁硅气凝胶接触角在113°～116°之间,比表面积可达589.79 m2/g,密度约为0.192 g/cm3,饱和磁化强度约为0.44 emu/g,具有超顺磁性。赋磁硅气凝胶对疏水性有机物异狄氏剂表现出良好的吸附性能,符合Freundlich等温吸附模型,KF为42.91;吸附动力学符合准二级动力学模型,吸附速率常数为0.0341 g/(mg.min)。     

Phenol electrooxidation on Fe-Co3O4 thin film electrodes in alkaline medium

Fe-Co₃O₄ thin film with different amounts of Fe have been used for the electro-oxidation of phenol in alkaline medium at room temperature. The electrodes were prepared by coating stainless steel supports with successive layers of the oxides, obtained by thermal decomposition at 673 K. The electrolysis was carried out at constant potential and the phenol disappearance, during the electrolysis, was monitored by UV-Vis absorbance measurements between 250 and 500 nm. After 3 h of electrolysis, the intermediates were identified by comparing the HPLC data and UV-Vis spectra to those from pure standards. The results indicate that the same oxidation products are formed on the different prepared electrodes, namely the decomposition products of phenol such as benzoquinone, hydroquinone and cathecol in basic medium. Simulated results show clearly the decrease of the amount of phenolic species with the electrolysis time. An enhancement of the phenol removal is observed with the presence of iron in the oxide. Under the operating conditions, around 30% of the initial phenol has been removed at ca. 3 h and the complete degradation is obtained after 54 h of electrolysis, when Fe-Co₃O₄ thin film with 10% of Fe is used as anode.     

Fe3O4/Ag磁性纳米颗粒去除水中的铅离子

采用水相共沉淀法制备小尺寸磁性Fe₃O₄纳米颗粒,以没食子酸作为还原剂和表面修饰剂,还原Ag[(NH₃)₂]⁺制备出Fe₃O₄/Ag磁性纳米颗粒。研究该磁性纳米颗粒对水溶液中铅离子的吸附行为,研究结果表明,pH为7.0,吸附温度30℃时可得到最好的处理效果,铅的去除率可达99.7%以上,Fe₃O₄/Ag颗粒吸附行为符合二级动力学模型(R² > 0.99)。该磁性纳米颗粒经过多次再生处理后,仍具有很好的吸附效果,表明Fe₃O₄/Ag在水处理方面拥有良好的应用前景。     

水滑石与磷酸银可见光催化剂的活性对比研究

本文合成了具备水滑石结构(LDH)的Zn-Cr LDH、Zn-Ti LDH以及Ag3PO43种半导体光催化剂,并对它们的催化性能进行对比研究。XRD和SEM分析表明,Zn-Cr LDH、Zn-Ti LDH具有层状结构而Ag3PO4呈纳米球状结构。UV-Vis分析表明,Ag3PO4和Zn-Cr LDH能够吸收可见光(>420 nm)。在可见光照射与添加AgNO3作为电子受体的条件下,Zn-TiLDH几乎没有光催化活性,而Ag3PO4的光催化活性高于Zn-Cr LDH。Ag3PO4在光解水实验中180 min内氧气产量约1.2mL,而Zn-Cr LDH约为0.65 mL。光催化降解有机污染物实验中,在Ag3PO4催化作用下,120 min内亚甲基蓝(MB)被完全降解,在240 min内46%的对硝基酚(PNP)被降解,而Zn-Cr LDH相应的去除率分别为61%和27%。     

含锰废渣的氧化-活化再生回用工艺

为实现紫苏醛生产过程中二氧化锰（氧化剂）的循环利用,采用一种新型的氧化-活化工艺再生得到活性二氧化锰,即以紫苏醇合成紫苏醛过程中产生的含锰废渣为原料,首先采用氯酸钠氧化含锰废渣得到初级二氧化锰,然后使用高锰酸钾对初级二氧化锰进一步活化得到活性二氧化锰。实验表明,制取初级二氧化锰的最佳工艺条件为：反应时间为4h,反应温度为90～95℃,硫酸摩尔浓度为1.5 mol/L,氯酸钠加量为理论量的130%。制取活性二氧化锰的合适条件为：反应温度在60℃时,反应时间为1.5 h;反应温度在50℃时,反应时间为2.5 h。采用氧化-活化法再生的活性二氧化锰氧化紫苏醇,紫苏醛的产率可达52.8%,与使用电解二氧化锰氧化得到的紫苏醛的产率53.1%相当,而使用初级二氧化锰,紫苏醛的产率仅为14.9%。     

O3、H2O2/O3及UV/O3在焦化废水深度处理中的应用

采用O₃、H₂O₂/O₃和UV/O₃等高级氧化技术(AOPs)对某焦化公司的生化出水进行深度处理,考察了O₃与废水的接触时间、溶液pH、反应温度等因素对废水COD去除率的影响,确定出O₃氧化反应的最佳工艺参数为：接触时间40 min,溶液pH 8.5,反应温度25℃,此条件下废水COD及UV₂₅₄的去除率最高可达47.14%和73.47%;H₂O₂/O₃及UV/O₃两种组合工艺对焦化废水COD及UV₂₅₄的去除率均有一定程度的提高,但H₂O₂/O₃系统的运行效果取决于H₂O₂的投加量。研究结论表明,单纯采用COD作为评价指标,并不能准确反映出O₃系列AOPs对焦化废水中有机污染物的降解作用。     

Simulated use and wash-off release of decamethylcyclopentasiloxane used in anti-perspirants

The cyclic volatile methylsiloxane, decamethylcyclopentasiloxane (D₅) is used in a large variety of personal care products. Based on the physical–chemical properties of D₅, it is likely that losses due to volatilisation may strongly influence the levels entering the aquatic environment. The aim of this study was to quantify the amount of D₅ in waste wash water, after typical application and use in a range of deodorant and anti-perspirant (AP) products. Results implied significant losses after a 24 h period (>99.9%), and suggest that the use of D₅ in leave-on products, such as deodorants/AP is not likely to contribute a significant down-the-drain emission source. An illustrative example is presented, based on data reporting the use of D₅ in a range of personal care products (both wash-off and leave-on), which suggests that the contribution of D₅ used in wash-off products to the aquatic environment may be considerably more significant. Limitations associated with our understanding of the actual D₅ inclusion levels in the products, the market share of the products containing D₅, and the variability of consumer habits, are identified as data gaps that need to be addressed in order to better refine down-the-drain emission estimates.     

磷酸微波活化多孔生物质炭对亚甲基蓝的吸附特性简

以甘蔗渣为原料,采用微波辅助H₃PO₄活化法制备富含含氧酸官能团的中孔生物质炭。通过扫描电子显微镜SEM、傅立叶变换红外光谱FT-IR等技术对生物质炭物理化学性质进行表征,并通过静态实验法,探讨炭样对亚甲基蓝的吸附行为及热力学性质。结果表明,H₃PO₄活化制备蔗渣生物质炭的适宜条件为浸渍比1：1,烘干时间10 h,活化功率900 W,活化时间22 min,在此条件下制得的生物质炭得率为39.2%,碘值为817 mg/g,亚甲基蓝值为229 mg/g,为国家一级品标准的1.7倍。红外光谱分析表明,炭样表面以羟基、羰基、羧基等酸性官能团为主。静态吸附实验表明,Freundlich方程与Redlich-Peterson方程能较好地描述等温吸附行为,表现为优惠吸附。热力学研究表明,吸附吉布斯自由能（ΔG⁰）<0,说明吸附反应是自发过程,而吸附标准焓变（ΔH⁰）>70 KJ/mol,表明亚甲基蓝在制备炭样上的吸附是吸热反应,升温有利于吸附,且化学反应在吸附过程中发挥了重要作用。     

Ca_5(AsO_4)_3OH的溶解度与稳定性研究

通过在不同pH值,温度等条件下Ca5(AsO4)3OH的溶解,确定其稳定存在的pH值范围,得出它的溶度积和生成的自由能(ΔG0f)。结果表明,Ca5(AsO4)3OH在水中的溶解度和稳定范围与pH和温度有关,在酸性条件下(初始pH=2)它的溶解度较大,而且在水中的溶解度随着温度的升高而降低。利用PHREEQC程序计算确定Ca5(AsO4)3OH的溶度积为10-40.86,生成自由能ΔG0f为-5 063.53 kJ/mol。利用JADE5软件计算得到其晶格参数a=b=9.696,c=6.967和晶胞体积为567.304 3。     

Reductive transformation of 2,4-dichlorophenoxyacetic acid by nanoscale and microscale Fe3O4 particles

Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe₃O₄ was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L^?1 nanoscale Fe₃O₄, and the reaction rates increased with increasing dosage of nanoscale Fe₃O₄. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe₃O₄ was slower than that by nanoscale Fe₃O₄. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

Results from a pilot-scale air quality study in Addis Ababa, Ethiopia

Twenty-one samples were collected during the dry season (26 January–28 February 2004) at 12 sites in and around Addis Ababa, Ethiopia and analyzed for particulate matter with aerodynamic diameter <10 μm (PM₁₀) mass and composition. Teflon-membrane filters were analyzed for PM₁₀ mass and concentrations of 40 elements. Quartz-fiber filters were analyzed for chloride, sulfate, nitrate, and ammonium ions as well as elemental carbon (EC) and organic carbon (OC) content. Measured 24-h PM₁₀ mass concentrations were <100 and 40 μg m⁻³ at urban and suburban sites, respectively. PM₁₀ lead concentrations were <0.1 μg m⁻³ for all samples collected, an important finding because the government of Ethiopia had stopped the distribution of leaded gasoline a few months prior to this study. Mass concentrations reconstructed from chemical composition indicated that 34–66% of the PM₁₀ mass was due to geologically derived material, probably owing to the widespread presence of unpaved roads and road shoulders. At urban sites, EC and OC compounds contributed between 31% and 60% of the measured PM₁₀ while at suburban sites carbon compounds contributed between 24% and 26%. Secondary sulfate aerosols were responsible for <10% of the reconstructed mass in urban areas but as much as 15% in suburban sites, where PM₁₀ mass concentrations were lower. Non-volatile particulate nitrate, a lower limit for atmospheric nitrate, constituted <5% and 7% of PM₁₀ at the urban and suburban sites, respectively. At seven of the 12 sites, real-time PM₁₀ mass, real-time carbon monoxide (CO), and instantaneous ozone (O₃) concentrations were measured with portable nephelometers, electrochemical analyzers, and indicator test sticks, respectively. Both PM₁₀ and CO concentrations exhibited daily maxima around 7:00 and secondary peaks in the late afternoon and evening, suggesting that those pollutants were emitted during periods associated with motor-vehicle traffic, food preparation, and heating of homes. The morning concentration maxima were likely accentuated by stable atmospheric conditions associated with overnight surface temperature inversions. Ozone concentrations were measured near mid-day on filter sample collection days and were in all cases <45 parts per billion.     

The use of experimental data and their uncertainty for assessing ozone photochemistry in the Eastern Iberian Peninsula

Observation-based methods are useful tools to explore the sensitivity of ozone concentrations to precursor controls. With the aim of assessing the ozone precursor sensitivity in two locations: Paterna (suburban) and Villar del Arzobispo (rural) of the Turia river basin in the east of Spain, the photochemical indicator O₃/NO_y and the Extent-of-Reaction (EOR) parameter have been calculated from field measurements. In Paterna, the O₃/NO_y ratio varied from 0 to 13 with an average value of 5.1 (SD 3.2), whereas the averaged value for the EOR was 0.43 (SD 0.14). In Villar del Arzobispo, the O₃/NO_y ratio changed from 5 to 30 with a mean value of 13.6 (SD 4.7) and the EOR gave an averaged value of 0.72 (SD 0.11). The results show two different patterns of ozone production as a function of the location. The suburban area shows a VOC-sensitive regime whereas the rural one shows a transition regime close to NO_x-sensitive conditions. No seasonal differences in these regimes are observed along the monitoring campaigns. Finally, an analysis of the influence of the measurement quality of NO_y, NO_x and O₃ on the uncertainty of the O₃/NO_y ratio and the EOR was performed showing that the uncertainty of O₃/NO_y is not dependent on either its value or the individual values of O₃ and NO_y but just on the quality of O₃ and NO_y measurements. The maximum uncertainty is 26% as long as the combined uncertainties of O₃ and NO_y remain below the 7.5%. The case of the EOR is different and its uncertainty depends on both the value of the EOR parameter and the individual concentration values of NO_y and NO_x. The uncertainty of the EOR estimation can be very high (>200%) if the combined uncertainties of both NO_y and NO_x are high (>7.5%), or especially, if u(NO_y) and u(NO_x) differ considerably from each other (>3.5%).     

Effect of variations in the redox potential of Gleysol on barium mobility and absorption in rice plants

Two assays were designed to obtain information about the influence of redox potential variations on barium mobility and bioavailability in soil. One assay was undertaken in leaching columns, and the other was conducted in pots cultivated with rice (Oryza sativa) using soil samples collected from the surface of Gleysol in both assays. Three doses of barium (100,300 mg kg⁻¹ and 3000 mg kg⁻¹-soil dry weight) and two redox potential values (oxidizing and reducing) were evaluated. During the incubation period, the redox potential (Eh) was monitored in columns and pots until values of −250 mV were reached. After the incubation period, geochemical partitioning was conducted on the barium using the European Communities Bureau of Reference (BCR) method. Rainfall of 200 mm d⁻¹ was simulated in the columns and in the planting of rice seedlings in the pots. The results of the geochemical partitioning demonstrated that the condition of reduction favors increased barium concentrations in the more labile chemical forms and decreased levels in the chemical forms related to oxides. The highest barium concentrations in leached extracts (3.36 mg L⁻¹) were observed at the highest dose and condition of reduction at approximately five times above the drinking water standard. The high concentrations of barium in the soil did not affect plant dry matter production. The highest levels and accumulation of barium in roots, leaves, and grains of rice were found at the highest dose and condition of reduction. These results demonstrate that reduction leads to solubilization of barium sulfate, thereby favoring greater mobility and bioavailability of this element.     

负载V2O5-WO3/TiO2掺炭纤维脱除烟气中Hg0

通过固定床实验系统研究烟气脱除零价汞的实验,首先研究了滤袋常用的聚苯硫醚（polyphenylene sulfide,PPS）以及活性炭纤维（activated carbon fiber,ACF）在不同温度、不同气体组分下负载V₂O₅-WO₃/TiO₂催化剂,对模拟燃煤烟气中零价汞（Hg⁰）的脱除效果。然后对比研究了活性炭纤维协同滤袋常用纤维负载催化剂后,对模拟燃煤烟气中Hg⁰的脱除性能。结果表明,在汞蒸气入口浓度为50 μg/m³,纯N₂气氛下,当温度为25℃时,两者脱除率均能达到99%,当温度为200℃,负载催化剂的活性炭纤维脱除率在30%左右,PPS纤维仅为10%左右。在200℃情况下,模拟烟气的组分为N₂+O₂时,2种纤维的Hg⁰脱除率提高了10%~20%,当在混合气体中添加0.01‰后,负载催化剂的PPS纤维Hg⁰脱除率能达到80%,活性炭纤维Hg⁰脱除率能达到98%。当温度为200℃,模拟烟气的组分为N₂+O₂+HCl时,不同性能掺炭纤维负载催化剂后Hg⁰脱除率在69%~95%范围之间变化,其中PPS掺炭纤维对Hg⁰脱除效率最高达到95%,因此,负载V₂O₅-WO₃/TiO₂催化剂的PPS掺炭纤维能在高温烟气中保持较高的Hg⁰脱除率。     

In situ measurement of isoprene in the marine air and surface seawater from the western North Pacific

Isoprene (2-methyl-1,3-butadiene) was measured on board of R/V Mirai for eight air samples and 14 seawater samples collected in the western North Pacific during ACE-Asia campaign (from 18 to 26 May 2001). The measurements were conducted in situ using a cryo-focus/gas chromatography/mass spectrometry (Cryo/GC/MS). Concentrations of isoprene ranged from 7.2 to 110 parts-per-trillion (pptv) in the marine air, and ranged from below 12 to 94 pmol l⁻¹ in the seawater. Based on these results, sea-to-air fluxes of isoprene were calculated to be 184 and 300 nmol m⁻² day⁻¹ for two samples, and the upper limits of the fluxes were also calculated to be from 32 to 300 nmol m⁻² day⁻¹. Atmospheric isoprene concentrations cannot be explained only by the flux from the seawater. Thus, the concentrations of isoprene in the marine air in western North Pacific should be significantly affected by terrestrial vegetational emission and subsequent long-range atmospheric transport of isoprene.     

Impact of biochar application to a Mediterranean wheat crop on soil microbial activity and greenhouse gas fluxes

Biochar has been recently proposed as a management strategy to improve crop productivity and global warming mitigation. However, the effect of such approach on soil greenhouse gas fluxes is highly uncertain and few data from field experiments are available. In a field trial, cultivated with wheat, biochar was added to the soil (3 or 6 kg m⁻²) in two growing seasons (2008/2009 and 2009/2010) so to monitor the effect of treatments on microbial parameters 3 months and 14 months after char addition. N₂O, CH₄ and CO₂ fluxes were measured in the field during the first year after char addition. Biochar incorporation into the soil increased soil pH (from 5.2 to 6.7) and the rates of net N mineralization, soil microbial respiration and denitrification activity in the first 3 months, but after 14 months treated and control plots did not differ significantly. No changes in total microbial biomass and net nitrification rate were observed. In char treated plots, soil N₂O fluxes were from 26% to 79% lower than N₂O fluxes in control plots, excluding four sampling dates after the last fertilization with urea, when N₂O emissions were higher in char treated plots. However, due to the high spatial variability, the observed differences were rarely significant. No significant differences of CH₄ fluxes and field soil respiration were observed among different treatments, with just few exceptions. Overall the char treatments showed a minimal impact on microbial parameters and GHG fluxes over the first 14 months after biochar incorporation.