区域空气质量模拟中查表法的应用研究

在自行开发完善的区域空气质量模式系统RegSRRMS中应用查表法,模拟中国典型城市群对流层大气主要污染物的浓度变化,评估该方法在大气复合污染事件预测和控制中的有效性.首先,利用具有国际先进水平的空气质量模式WRF-CHEM中的化学模块建立了包含完善气相化学、气溶胶过程的箱模式WRFBOX.其次,利用WRFBOX进行化学反应敏感性分析,基于影响污染物的重要因子分别建立了臭氧(O3)及其前体物、无机盐气溶胶和二次有机气溶胶(SOA)查算表数据库,并检验其有效性.最后,将此查算表数据库引入RegSRRMS,建立简化的查表算法.利用直接耦合机制法和查表法对2000年3月珠三角地区污染个例中主要大气污染物浓度进行模拟.通过比较2种方法的模拟结果,显示查表法计算效率提高了57%,能够反映大气光化学反应的非线性特征、气溶胶及其前体物的平衡关系,具有高分辨率、高时效性,能够方便快捷地给出源和受体之间的响应关系,结果可靠.在区域空气质量模式中应用查表法有利于大气污染事件的快速预测以及大气污染控制的快速决策.     

络合-超滤耦合工艺去除水中镍离子的研究

以聚丙烯酸钠(PAANa)和聚乙烯亚胺(PEI)作为络合剂,将其与镍离子络合后的溶液转移至超滤杯中,在0.1 MPa压力下通过聚醚砜超滤膜进行分离,研究pH值和络合剂/Ni2+装载质量比(L)对Ni2+去除率的影响,并根据朗缪尔等温模型拟合络合反应平衡常数.同时研究超滤时间对膜通量和Ni2+去除率的影响.结果表明,选用PAANa为络合剂,在pH值为8、L=5时,Ni2+的去除率达到最大值99.5%.PEI为络合剂时,Ni2+去除率在pH值为7、L为5时达到最大值93.0%.不同pH值条件下拟合得到的络合平衡常数表明,pH为7时最有利于络合反应.另外,单个络合剂单体所能结合的Ni2+个数随着pH值的升高而增大.研究结果还表明,在长达12 h的超滤时间内,PAANa为络合剂时,膜通量的衰减<10%;PEI为络合剂时,膜通量基本保持不变;Ni2+的去除率都基本保持恒定.因此,在合适条件下,络合-超滤耦合工艺能有效去除水中的镍离子.     

Effects of long-term amendment of organic manure and nitrogen fertilizer on nitrous oxide emission in a sandy loam soil

To understand the effects of long-term amendment of organic manure and N fertilizer on N2O emission in the North China Plain, a laboratory incubation at different temperatures and soil moistures were carried out using soils treated with organic manure （OM）, half organic manure plus half fertilizer N （HOM）, fertilizer NPK （NPK）, fertilizer NP （NP）, fertilizer NK （NK）, fertilizer PK （NK） and control （CK） since 1989. Cumulative N2O emission in OM soil during the 17 d incubation period was slightly higher than in NPK soil under optimum nitrification conditions （25℃ and 60% water-filled pore space, WFPS）, but more than twice under the optimum denitrification conditions （35℃ and 90% WFPS）. N2O produced by denitrification was 2.1-2.3 times greater than that by nitrification in OM and HOM soils, but only 1.5 times greater in NPK and NP soils. These results implied that the long-term amendment of organic manure could significantly increase the N2O emission via denitrification in OM soil as compared to NPK soil. This is quite different from field measurement between OM soil and NPK soil. Substantial inhibition of the formation of anaerobic environment for denitrification in field might result in no marked difference in N2O emission between OM and NPK soils. This is due in part to more rapid oxygen diffusion in coarse textured soils than consumption by aerobic microbes until WFPS was 75% and to low easily decomposed organic C of organic manure. This finding suggested that addition of organic manure in the tested sandy loam might be a good management option since it seldom caused a burst of N2O emission but sequestered atmospheric C and maintained efficiently applied N in soil.     

Determination of alkali-labile phosphoprotein phosphorus from fish plasma using the Tb^3＋-tiron complex as a fluorescence probe

A sensitive method based on the fluorescence quenching effect of the Tb^3＋-Tiron complex is proposed for the determination of alkali-labile phosphoprotein phosphorus （ALP） released from fish plasma. The detection limit was 5.4 ng/ml （S/N=2）, and the relative standard deviation of the quenching effect （6 replicates） was 4.6%. The results obtained by the proposed method were in good agreement with those obtained by the colorimetric assay. The advantages of the present method are its relatively simple detection procedure, the lack of toxic organic solvents, and high sensitivity.     

Characterizing ionic species in PM2:5 and PM10 in four Pearl River Delta cities, South China

PM_(2.5)and PM_(10)samples were collected at four major cities in the Pearl River Delta(PRD),South China,during winter and summer in 2002.Six water-soluble ions,Na~ ,NH_4~ ,K~ ,Cl~-,NO_3~- and SO_4~(2-)were measured using ion chromatography.On average,ionic species accounted for 53.3% and 40.5% for PM_(2.5)and PM_(10),respectively in winter and 39.4% and 35.2%,respectively in summer. Secondary ions such as sulfate,nitrate and ammonium accounted for the major part of the total ionic species.Sulfate was the most abundant species followed by nitrate.Overall,a regional pollution tendency was shown that there were higher concentrations of sulfate, nitrate and ammonium in Guangzhou City than those in the other PRD cities.Significant seasonal variations were also observed with higher levels of species in winter but lower in summer.The Asian monsoon system was favorable for removal and diffusion of air pollutants in PRD in summer while highly loading of local industrial emissions tended to deteriorate the air quality as well.NO_3~-/SO_4~(2-) ratio indicated that mobile sources have considerably contribution to the urban aerosol,and stationary sources should not be neglected. Besides the primary emissions,complex atmospheric reactions under favorable weather conditions should be paid more attention for the control of primary emission in the PRD region.     

Kinetics of selective catalytic reduction of NO by NH3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results show that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3, respectively, at 350-450℃. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.     

Mn对超富集植物短毛蓼和水蓼生长、Mn吸收及氮素代谢的影响

采用水培的方法,研究了不同浓度Mn(0.0003、0.5、1、2、4、8 mmol · L^-1)对Mn超富集植物短毛蓼(Polygonum pubescens Blume)和水蓼(Polygonum hydropiper L.)叶片铵态氮、硝态氮、游离脯氨酸、可溶性蛋白质含量及氮素代谢关键酶:硝酸还原酶(NR)、谷氨酰胺合成酶(GS)、谷氨酸合酶(GOGAT)和谷氨酸脱氢酶(GDH)活性的影响.结果表明,随着Mn处理浓度的增加,短毛蓼和水蓼的根、茎、叶中Mn含量显著增加(p<0.05),在相同Mn处理浓度下短毛蓼中Mn含量均大于同部位水蓼中Mn含量.在Mn处理浓度小于1 mmol · L^-1时,Mn对短毛蓼的株高、株重影响不显著,但对水蓼的影响显著(p<0.05),表明短毛蓼比水蓼更耐Mn污染.Mn处理显著降低了短毛蓼硝态氮含量(p<0.05),提高了可溶性蛋白质含量,浓度为8 mmol · L^-1的Mn处理显著提高了水蓼硝态氮、铵态氮、可溶性蛋白质含量及短毛蓼、水蓼游离脯氨酸含量(p<0.05).Mn引起了短毛蓼和水蓼氮素代谢关键酶活性的变化,显著降低了水蓼叶片NR、短毛蓼叶片GS活性(p<0.05);在Mn处理浓度为1 mmol · L^-1时,短毛蓼叶片NR活性最高,为对照的1.91倍,而2、4、8 mmol · L^-1 Mn处理显著降低了短毛蓼和水蓼GOGAT活性(p<0.05).另外,Mn处理显著提高了短毛蓼和水蓼叶片GDH活性(p<0.05),在Mn处理浓度为8 mmol · L^-1时,短毛蓼、水蓼叶片GDH活性分别为对照的16.29倍和1.29倍.     

Effect of C/N ratio, aeration rate and moisture content on ammonia and greenhouse gas emission during the composting

Gaseous emission (N₂O, CH₄ and NH₃) from composting can be an important source of anthropogenic greenhouse gas and air pollution. A laboratory scale orthogonal experiment was conducted to estimate the effects of C/N ratio, aeration rate and initial moisture content on gaseous emission during the composting of pig faeces from Chinese Ganqinfen system. The results showed that about 23.9% to 45.6% of total organic carbon (TOC) was lost in the form of CO₂ and 0.8% to 7.5% of TOC emitted as CH₄. Most of the nitrogen was lost in the form of NH₃, which account for 9.6% to 32.4% of initial nitrogen. N₂O was also an important way of nitrogen losses and 1.5% to 7.3% of initial total nitrogen was lost as it. Statistic analysis showed that the aeration rate is the most important factor which could affect the NH₃ (p = 0.0189), CH₄ (p = 0.0113) and N₂O (p = 0.0493) emissions significantly. Higher aeration rates reduce the CH₄ emission but increase the NH₃ and N₂O losses. C/N ratio could affect the NH₃ (p = 0.0442) and CH₄ (p = 0.0246) emissions significantly, but not the N₂O. Lower C/N ratio caused higher NH₃ and CH₄ emissions. The initial moisture content can not influence the gaseous emission significantly. Most treatments were matured after 37 days, except a trial with high moisture content and a low C/N ratio.     

Roles of manganese oxides in degradation of phenol under UV-Vis irradiation: Adsorption, oxidation, and photocatalysis

The effect of crystal structure on photocatalytic activities of manganese oxides and underlying reaction mechanism were investigated.     

La-Co-Fe-Cu/HZSM-5在尾气碳颗粒燃烧中的催化性能

采用柠檬酸络合低温浸渍法制备分子筛负载钙钛矿型复合氧化物催化剂。采用XRD、SEM和H2-TPR等手段对催化剂性能进行表征,并在微型固定床反应器中对催化剂进行活性评价。结果表明,在钙钛矿型复合氧化物中进行B位离子掺杂,可以改善催化活性,碳颗粒燃烧温度降低。在20%LaCoO3/HZSM-5催化剂中用铁离子部分取代钴离子可以改善碳颗粒的燃烧性能,取代量增加碳颗粒燃烧温度降低,但是生成CO2的选择性也降低,以20%LaCo0.2Fe0.8O3/HZSM-5为催化剂,Tig、Tm和Tf分别为256℃、399℃和403℃,但生成CO2的选择性只有72.5%。在20%LaCo1-xFexO3/HZSM-5中的钙钛矿型复合氧化物B位离子中加入铜离子后,在碳颗粒燃烧反应中生成CO2的选择性得到明显改善,Sco2提高10个单位以上。以20%LaCo0.2Fe0.6Cu0.2O3/HZSM-5为催化剂,在碳颗粒燃烧反应中生成CO2的选择性可以达到94.7%,Tig、Tm和Tf分别为242℃、427℃和445℃。