影响柴油在土壤中挥发的因素

石油污染物进入土壤中后经历一系列物理化学和生物过程,其中发生的挥发过程是一种重要的迁移过程。本文以柴油为石油污染物的代表,研究了温度及土壤质地对柴油挥发行为的影响。通过在不同温度下纯柴油的挥发及柴油从四种不同土质的薄层土壤中的挥发试验,对柴油的挥发量与挥发时间的关系进行了模拟,结果表明:在不同温度下,纯柴油及柴油在四种薄层土壤中的挥发量与挥发时间的关系均可采用二次多项式来拟合。通过对比经相近时间柴油从4种不同土壤表面的挥发后,发现柴油挥发量均大于从纯柴油时的挥发量。在有机质质量分数不同的土壤中进行了柴油挥发试验,结果表明高有机质会抑制土壤中的柴油的挥发。     

新疆盐渍化土壤氮肥氨挥发损失特征初步研究

在室温下应用“静态吸收法”,研究不同盐渍化程度的盐化土壤和碱化土壤上氮肥氨挥发损失特征。结果表明:(1)除碱土外碱化土壤上氮肥氨挥发量随时间延长呈现下降趋势,在盐化土壤上氨挥发量随时间呈现先上升后下降趋势。(2)供试9个典型盐渍化土壤样品上氮肥氨挥发量(Y)与时间(t)关系均符合Y=at2 bt c动力学方程,相关性呈极显著水平。(3)氨挥发总量(Y)、氨挥发速率(Yi)与土壤含盐量(x)呈极显著正相关;氨挥发持续时间随着盐渍化程度的增加而延长。(4)氨挥发总量、挥发速率与盐渍土pH相关性未达到显著水平;盐渍土上pH值对氨挥发的影响需要进一步研究。以上结果表明,盐渍化耕作土壤上氮肥氨挥发的控制要依据盐渍化类型的不同而制定相应的措施。     

氮肥施用对西藏青稞产量及氨挥发损失的影响

为了解西藏农田系统氮肥施用对青稞产量和氨挥发氮损失的影响规律,通过田间随机区组试验,设置了N0～N3共4个施氮水平,采用田间原位测定-通气法,研究了土壤氨挥发通量、变化规律及其与产量的关系。结果表明:青稞产量与施氮量呈显著正相关(P0.05),氮肥贡献率高达32.13%,氮肥农学效益为3.62～4.78 kg·kg~(-1)。氨挥发总累积量为3.38～21.51 kg·hm~(-2),氨挥发导致的氮肥损失率为10.75%～15.49%,与施氮量呈极显著相关(P0.01)。青稞农田氨挥发主要发生在基肥期,基肥氨挥发周期44 d,第10天开始陆续出现挥发峰,追肥氨挥发集中在施肥后7 d内。综合考虑生产效益和以氨挥发为指标的环境安全,该区域青稞农田纯N建议施用量为:基肥40.02 kg·hm~(-2),拔节追肥13.32～26.70 kg·hm~(-2),抽穗追肥40.02 kg·hm~(-2)。     

基于RZWQM模型的华北平原冬小麦-夏玉米土壤硝态氮淋溶和氨挥发评估方法研究

硝态氮淋溶和氨挥发是华北平原农田因施肥所引起的最重要的氮损失途径,直接监测法的过程复杂且需要消耗大量人力物力,如何建立科学准确的损失量与土壤性质之间的关系,以支撑管理部门便捷快速估算各途径氮损失量成为迫切需要解决的问题。利用已经通过华北平原冬小麦-夏玉米长期定位试验数据进行参数率定验证的RZWQM模型,输出不同施肥水平下1 m内土壤硝态氮残留量、硝态氮淋溶量和氨挥发量,通过回归分析构建了土壤硝态氮淋溶量和氨挥发量分别与1 m内土壤硝态氮残留量之间的函数关系,并利用华北地区研究文献中实测数据对函数准确率进行分析,得出在华北平原2个函数平均准确率分别为70. 9%和71. 2%,该方法可供管理部门在估算和管理华北地区面源污染发生量过程中推广使用。     

气化熔融处理生活垃圾时灰渣的熔融特性

弄清垃圾灰渣的熔融特性对于保证生活垃圾的气化熔融与液态出渣具有重要作用。针对重庆生活垃圾灰与无烟煤灰形成的灰渣,实验研究了在不同的燃料添加量及添加剂条件下灰渣的熔点与粘度,并结合炉温的变化,分析了不同条件对灰渣熔融及液态出渣的影响。结果表明,灰渣的熔点与粘度均随燃料添加量的增加而升高;向燃料比为10%的灰渣中加入添加剂后,灰渣的熔点降低幅度较小,其粘度却随碱度的增加而增大以至熔渣流动性变差;燃料比为40%时,灰渣熔点与粘度均随添加剂的加入而显著降低,且向渣中加入CaO使得灰渣碱度为1.2时灰渣熔点较低且粘度较小,有利于其熔融与液态出渣。     

太湖地区稻田氮素损失特征及环境效应分析

通过氮肥减量小区试验,研究了太湖地区稻田氮素径流损失、渗漏损失、氨挥发损失以及氨挥发通量的动态变化特征,阐述了氮素损失量、水稻产量与施氮量之间的关系。结果表明：稻季氮素径流损失和氨挥发损失均随施氮量的增加不断增加,而渗漏损失与施氮量没有显著相关性。综合整个稻季,氨挥发损失以分蘖肥期最高,基肥期次之,穗肥期最低。稻季氮素总损失为13.7～59.8 kg·hm-2,占总施氮量的16.5%～22.2%,且随施氮量的增加而不断增加,其中氨挥发损失占42.2%～72.0%,径流损失占22.2%～38.4%,渗漏损失占5.8%～22.7%。稻季181 kg·hm-2的氮肥用量,较常规施氮量减少了33%的氮肥,增加了10.3%的产量,降低了48.5%的氮素损失,较好地兼顾了粮食产量和环境效应;而对于重要环境区域或高污染区域,还可以尝试更低的氮肥投入,以达到更好的环境效益。     

紫花苜蓿在柴油污染土壤中的萌发状况

选择以柴油作为土壤污染物，以单-外源环境因子污染水平为主要调控因子，采用室内盆栽试验的方法并且以不同质量分数的柴油污染土壤，在此情况下观察不同土壤柴油污染质量分数控制下紫花苜蓿种子的萌发与生长情况。结果表明，紫花苜蓿种子发芽抑制率与土壤柴油污染质量分数呈现指数线性相关关系，并且发现苜蓿发芽之后，高质量分数柴油处理组的幼苗出现黄叶和干枯现象。文章最后从土壤内柴油和柴油在土壤-大气界面间的迁移对种子萌发的影响进行了探讨。     

水中苯挥发引起的热力学焓变过程

利用水槽试验对苯的挥发特性进行研究,在此基础上,通过数值计算探求苯在挥发过程中热力学因素焓的变化规律.结果表明,焓变的时空变化与浓度的时空变化密切相关.随挥发时间的增加,苯浓度下降,焓变的数值也越来越小;随水流下移,苯浓度峰值下移,焓变峰值的位置也不断下移;随着铅垂高度Y的增加,苯的扩散速度增大,焓变值不断减小;而在同一时刻,在宽度Z方向,焓变的数值曲线都呈阶梯性变化.     

醇-柴油间界面张力及对砂柱柴油去除率的影响

研究了四种醇类助溶剂表面/界面张力随浓度的变化,表面张力与界面张力之间的关系,以及界面张力降低对残油去除率的影响,结果表明,醇的浓度与表面张力之间满足Szyskowski模型,与界面张力间呈对数函数关系,用Fowkes模型计算乙醇溶液的色散力与理论预测具有一致性,四种醇对油水界面降低能力的顺序为:丁醇＞异丙醇＞乙醇＞异丁醇,醇溶液-柴油界面张力基本上不随时间发生变化;乙醇对含油砂柱冲洗试验结果表明除油率与界面张力降低呈指数关系.     

土壤中不同老化时间的DDT对小麦根系的生物有效性

研究了水、正己烷、正己烷/丙酮ASE对土壤中不同老化时间的DDT的逐级提取量的差别及其与小麦根吸收的关系。结果表明,有机氯的水提量随老化时间增加而下降,正己烷提取量随老化时间增加而下降,正己烷/丙酮提取量随老化时间增加而上升。植物根吸收随老化时间增加而下降。根吸收与水提量没有确定关系,与正己烷提取量具正相关关系,与正己烷/丙酮提取量有负相关关系。正己烷提取量可被作为土壤有机氯DDT的有效态部分。     

柴油污染土壤生物修复对土壤酶活性的影响

在柴油污染土壤的生物修复过程中,分析了土壤中柴油降解菌数量和3种土壤酶活性(过氧化氢酶、脱氢酶和脂酶)等生物活性指标与土壤中柴油去除率的相关性.结果表明,土壤受到柴油污染后的一段时间后过氧化氢酶、脱氢酶和脂酶的活性上升,而后随着土壤中石油烃的降解,脂酶又不断降低.进一步分析表明脂酶活性与柴油降解率及柴油降解菌数量都具有很好的正相关性,可以采用土壤脂酶活性来指示柴油生物降解成效.     

Effect of Diesel Fuel on Growth of Selected Plant Species

Diesel oil is a complex mixture of hydrocarbons with an average carbon number of C8–C26. The majority of components consist of alkanes, both straight chained and branched and aromatic compounds including mono-, di- and polyaromatic hydrocarbons. Regardless of this complexity, diesel oil can be readily degraded by a number of soil microorganisms making it a likely candidate for bioremediation. The concept of using plants to enhance bioremediation, termed phytoremediation, is a relatively new area of scientific interest. It is particularly applicable to diesel oil contamination as diesel oil generally contaminates the top few metres of soil (surface soil) and contamination is not uniform throughout the site. By encouraging plants to grow on diesel oil contaminated soil, conditions are improved for the microbial degradation of the contaminant. During this study, establishing plants on diesel oil contaminated soil proved difficult. Diesel oil is phytotoxic to plants at relatively low concentrations. At concentrations below this phytotoxic level, the development of plants grown in diesel oil contaminated soil differs greatly from plants grown in uncontaminated soil. Tolerance of plants to diesel oil and ability to germinate in diesel oil contaminated soil varied greatly between plant species as well as within plant species. The broadest differences in germination were seen within the grasses with certain species thriving in low levels of contamination (e.g. Creeping bent) while others were intolerant of diesel oil contamination (e.g. Rough meadow grass). The herbs, legumes and commercial crops screened appeared to be largely unaffected by low levels of diesel oil contamination (25g dieselkg^–1). At the higher level of contamination (50g dieselkg^–1), half of the twenty two plants species screened failed to reach a germination rate equal to 50% of the control rate. Two species of grass failed to germinate at all at this contamination level. Plant species that successfully germinated and grew were studied further to determine the effect of diesel oil contamination on the later stages of plant development. This work investigates the effect of diesel oil on plant growth and development.     

Polynuclear aromatic compounds in kerosene,diesel and unmodified sunflower oil and in respective engine exhaust particulate emissions

Polynuclear aromatic compounds (PAC) were characterized in diesel fuel, kerosene fuel and unmodified sunflower oil as well as in their respective engine exhaust particulates. Diesel fuel was found to contain high amounts of different PAC, up to a total concentration of 14,740?ppm, including carbazole and dibenzothiophene, which are known carcinogens. Kerosene fuel was also found to contain high amounts of different PAC, up to a total concentration of 10,930?ppm, consisting mainly of lower molecular weight (MW) naphthalene and its alkyl derivatives, but no PAC component peaks were detected in the unmodified sunflower oil. Engine exhaust particulates sampled from a modified one-cylinder diesel engine running on diesel, kerosene and unmodified sunflower oil, respectively, were found to contain significantly high concentrations of different PAC, including many of the carcinogenic ones, in the soluble organic fraction (SOF). PAC concentrations detected at the exhaust outlet indicated that most of the PAC that were present in diesel and kerosene fuels before the test runs got completely burnt out during combustion in the engine whereas some new ones were also formed. The difference between the character and composition of PAC present in the fuels and those emitted in the exhaust particulates indicated that exhaust PAC were predominantly combustion generated. High amounts of PAC, up to totals of 52,900 and 4830?µg?m^?3 of burnt fuel, in diesel and kerosene exhaust particulates, respectively, were detected in the dilution tunnel when the exhaust emissions were mixed with atmospheric air. Significant amounts of PAC were also emitted when the engine was run on unmodified sunflower oil with a total concentration of 17,070?µg?m^?3 of burnt fuel detected in the dilution tunnel. High proportions of the combustion-generated PAC determined when the engine was run on diesel, kerosene and unmodified sunflower, respectively, consisted of nitrogen-containing PAC (PANH) and sulphur-containing PAC (PASH).     

Impact of biochar produced from post-harvest residue on the adsorption behavior of diesel oil on loess soil

The primary objective of this study was to investigate the effect of biochar, produced from wheat residue at different temperatures, on the adsorption of diesel oil by loess soil. Kinetic and equilibrium data were processed to understand the adsorption mechanism of diesel by biochar-affected loess soil; dynamic and thermodynamic adsorption experiments were conducted to characterize this adsorption. The surface features and chemical structure of biochar, modified at varying pyrolytic temperatures, were investigated using surface scanning electron microscopy and Fourier transform infrared analysis. The kinetic data showed that the adsorption of diesel oil onto loess soil could be described by a pseudo-second-order kinetic model, with the rate-controlling step being intraparticle diffusion. However, in the presence of biochar, boundary layer control and intraparticle diffusion were both involved in the adsorption. Besides, the adsorption equilibrium data were well described by the Freundlich isothermal model. The saturated adsorption capacity weakened as temperature increased, suggesting a spontaneous exothermic process. Thermodynamic parameter analysis showed that adsorption was mainly a physical process and was enhanced by chemical adsorption. The adsorption capacity of loess soil for diesel oil was weakened with increasing pH. The biochar produced by pyrolytic wheat residue increased the adsorption behavior of petroleum pollutants in loess soil.

     

0~#柴油和流花原油对斑节对虾(Penaeus monodon)幼体的急性毒性效应

溢油污染导致的原油和燃料油入海,会对海洋生物的生长发育过程产生影响。为研究溢油污染对海洋虾类的毒性效应,以斑节对虾(Penaeus monodon)为研究对象,比较了不同浓度0#柴油和南海流花原油(LH原油)乳化液对斑节对虾不同发育阶段幼体的急性毒性效应。结果表明,3.59 mg·L~(-1)0#柴油和0.77 mg·L~(-1)LH原油乳化液可以显著降低斑节对虾无节幼体变态率(P0.05),且对无节幼体变态具有延迟效应。较之0#柴油,LH原油乳化液对斑节对虾无节幼体发育的影响更为明显。0#柴油对斑节对虾无节幼体、蚤状幼体、糠虾和仔虾的48或96小时半致死浓度(48 h/96 h-LC50)分别为0.55 mg·L~(-1)、0.42 mg·L~(-1)、0.95 mg·L~(-1)和1.09 mg·L~(-1),其对应的安全浓度分别为0.05 mg·L~(-1)、0.04 mg·L~(-1)、0.10 mg·L~(-1)和0.11 mg·L~(-1);LH原油对上述幼体的48 h/96 h-LC50则依次为0.62 mg·L~(-1)、0.51 mg·L~(-1)、1.05 mg·L~(-1)和1.42 mg·L~(-1),对应的安全浓度分别为0.06 mg·L~(-1)、0.05mg·L~(-1)、0.11 mg·L~(-1)和0.14 mg·L~(-1)。斑节对虾不同发育阶段幼体对0#柴油和LH原油的耐受力依次为:仔虾糠虾无节幼体蚤状幼体,0#柴油和LH原油乳化液对斑节对虾的毒性大小为0#柴油LH原油。上述结果为深入研究石油类污染对海洋生物的毒性效应提供了基础数据和理论依据。     

Pyrolysis behaviors of oil sludge based on TG/FTIR and PY-GC/MS

Pyrolysis is an alternative technology for oil sludge treatment. Thermogravimetric Analysis-Fourier Transform Infrared Spectroscopy and Pyrolysis-Gas Chromatography/Mass Spectrometry were employed to investigate the pyrolysis process and products of oil sludge. The pyrolysis process was divided into five stages: drying and gas desorption, oil volatilization, main pyrolysis, semi-coke charring, and mineral decomposition. The main reaction temperatures ranged from 497.6 K to 753.2 K. The products were mainly composed of pairs of alkane and alkene (carbon number ranges from 1 to 27). The mechanisms consisted of random chain scission followed by end chain scission at high temperatures with volatilization occurring during the whole process. This study is useful not only for the proper design of a pyrolysis system, but also for improving the utilization of liquid oil products.     

Tiefentschwefelte Kraftstoffe

In recent years, much attention has been given to the desulphurization of fuels like diesel oil and gasoline, since exhaust gases containing SOx cause air pollution and acid rain. Moreover, a lower sulphur content of fuels would allow the use of new engines and catalytic systems for the reduction of CO, particle and NOx-emissions, and a more efficient fuel consumption. The S-level in fuels is presently limited in Germany for gasoline and diesel oll to 150 ppm and 350 ppm, respectively. In 2005 the level will be decreased Europe-wide for all vehicle-fuels down to 50 ppm; in some countries, fuels are or will be on the market with even less sulphur. The current technology of hydrodesulphurization (heterogeneous, catalyzed hydrorreating of organic sulphur compounds) can desulphurize quite adequately down to today’s S-level. The process, however, is limited for the production of ultra-low sulphur fuels, and the expenses (pressure, reactor size, investment costs, energy consumption, specific active catalysts) are high to meet future requirements. alternative processes, which are not limited to hydrotreating, are therefore desirable. Beside an overview about hydrotreating, this paper presents two quite different alternatives: Extraction of sulphur compounds by ionic liquids and the synthetic production of S-free fuels from natural gas by Fischer-Tropsch-synthesis. Ionic liquids (ILs) are low melting (<100°C) salts which represent a new class of non-molecular, ionic solvents. In the experiments presented, extraction of model diesel oils (dibenzothiophene and dodecanthiol in n-dodecane) as well as of a real predesulphurized diesel oil (with about 400 ppm S) were investigated. The results show the excellent and selective extraction properties of ILs for organic sulphur compounds, especially with regard to those compounds which are very difficult to remove by common hydrodesulphurization. As expected, the desulphurization by extraction is much more complicated in case of real diesel oil (compared to a model oil) due to its complex chemical composition including many different sulphur compounds and other impurities like organic nitrogen and metal-compounds. Nevertheless, the results with pre-desulphurized diesel oil are also very promising. So, extraction of sulphur components by ILs is a new approach for deep desulphurization of diesel oil. The application of very mild process conditions (low pressure and temperature) in comparison to traditional hydrotreating is an additional advantage of this new concept. An alternative to today’s fuels based on crude oil is the production of gasoline and diesel oil from natural gas (or other fossil fuels like coal) by Fischer-Tropsch-synthesis (FTS). The products like diesel oil are completely free of sulphur and other impurities like nitrogen and metal compounds. Although several FTS-processes have been investigated and developed, and some processes are already running on a technical scale, a real breakthrough was not obtained up to now. The production costs of these capital-intensive processes are probably above the breakeven point, at least at today’s oil price. In this paper, a ‘lowcost’ process is discussed, which is based on nitrogen-rich syngas. In contrast to classical FTS-processes with nitrogen-free syngas, the investment costs are probably lower: The syngas is produced by partial oxidation with ait, which eliminates the need of an air separation plant, while a process with nitrogen-rich syngas does not utilize a recycle loop and a recycle compressor.     

表面活性剂对柴油在土壤中吸附的影响

通过静态吸附实验,研究土壤对十二烷基苯磺酸钠(LAS)和十六烷基三甲基溴化铵(CTAB)的吸附行为,探讨表面活性剂对柴油吸附的影响.结果表明,土壤对LAS和CTAB的吸附等温线均为非线性,其吸附能力的大小顺序为:轻壤土>轻粘土>中壤土>砂壤土>重壤土>紧砂土.同一土壤中,CTAB的吸附量大于LAS的吸附量.LAS和CTAB均利于柴油在土壤表面的解吸,且LAS的解吸效果更好.柴油的吸附量随LAS浓度的升高而降低.当CTAB的浓度小于临界胶束浓度CMC时,吸附量随CTAB浓度的升高而升高,当CTAB的浓度等于或大于临界胶束浓度(CMC)时,吸附量随CTAB浓度的升高而降低.