土壤生态系统微量元素的生物有效性研究现状

土壤中植物必需的微量营养元素的供给以及有害元素的毒性大小并不仅仅与元素的总量有关,而取决于元素的有效性。文章论述了元素生物有效性的含义,介绍了元素有效性的研究方法,即连续偏提取法和单提取法,并对一些相关问题进行了深入的分析讨论。     

芬顿与氧化钙联合处理填埋库污泥的力学特性

面对城市生活污泥填埋库容趋于饱和的现状,亟需研究开发城市生活污泥的减量化及资源化技术。以填埋库污泥和新鲜污泥为研究对象,进行岩土工程特性实验,发现填埋库污泥有机质含量及含水率远低于新鲜污泥。通过固结实验和直剪实验,分别对比、分析了未加药剂的填埋库污泥和药剂调质填埋库污泥的固结系数、渗透系数和抗剪强度变化规律。结果表明：填埋库污泥在pH为4时,芬顿试剂(硫酸亚铁和过氧化氢)的最佳配比为Fe²⁺=8%、H₂O₂=12%;当氧化钙投加量增加时,调质污泥的压缩指数减小,抗剪强度略微增大;考虑到联合处理后污泥的资源化利用、强碱性对环境的影响和处理成本,在实际污泥处理工程中,氧化钙投加量15%是较为合适的添加量,且效果优于常用的氯化铁药剂调制污泥。经芬顿与氧化钙联合处理的填埋库污泥抗剪强度满足填埋库要求,能够实现减容减量,对填埋库污泥后续资源化利用具有一定的指导意义。     

垃圾填埋场渗滤液物化深度处理研究

通过Fenton法和结合聚合硫酸铁的混凝作用,实现垃圾渗滤液氧化塘出水COD的深度处理;并利用水泥水化产物的凝胶物质,强化COD去除率。30％H2O2投加量为0．75mL／L、七水硫酸亚铁投加量为1．5g／L、n（H2O2）：n（Fe^2＋）=1．2：1（摩尔比）时,Fenton法对渗滤液COD的去除率可达52％;水灰比为2：1、搅拌24h的水泥水化物将Fenton法的出水pH值从4调至10,该工艺流程总的COD去除率为73．6％,较普通的Ca（OH）2调节法提高9．3％,出水COD可以从进水的1200mg／L降至315mg／L。     

混凝与Fenton联用处理垃圾渗滤液的效能及成本

为对混凝/Fenton工艺与Fenton/混凝工艺处理垃圾渗滤液的效果和成本进行比较,分别对年轻渗滤液和老龄渗滤液原液按照混凝/Fenton工艺与Fenton/混凝工艺2种技术路线进行处理。实验结果表明,Fenton试剂对年轻垃圾渗滤液和老龄垃圾渗滤液COD去除率最高的反应条件为pH=3.5、H2O2和Fe2+的摩尔比为6、H2O2和渗滤液原液的COD质量比为3、反应时间4 h;在PAC与渗滤液原液的COD质量比为0.6时,PAC混凝对渗滤液原液的COD去除率最高。在对渗滤液COD去除率最高的Fenton反应和PAC混凝反应条件下,混凝/Fenton工艺对年轻渗滤液和老龄渗滤液的COD去除率分别为90.56%和86.56%;Fenton/混凝工艺对年轻渗滤液和老龄渗滤液的COD去除率分别为89.99%和85.99%,2种技术路线对渗滤液COD的去除率相差不大,但先PAC混凝后Fenton氧化工艺比先Fenton后混凝工艺每t节省62.6元,是更优化的渗滤液处理工艺。     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Gas/particle partitioning of atmospheric PCDD/Fs in a satellite town in Eastern China

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air was investigated in a satellite town in Eastern China from April 2007 to January 2008 comprehending large temperature variations (from 3 to 34 °C, daily average). Molecular weight, molecular structure and ambient temperatures are the three major factors that govern the gas/particle partitioning of atmospheric PCDD/Fs throughout the year. Generally, good agreements were obtained (except for winter) between measured particulate fractions and theoretical estimates of both the Junge–Pankow adsorption model and Harner Bidleman absorption model using different sets of subcooled liquid vapor pressure and octanol–air partition coefficient (K_oa), respectively. Models utilizing estimates, derived from gas chromatographic retention indices (GC-RIs), are more accurate than that of entropy-based. Moreover, during winter, the K_oa-based model using the GC-RIs approach performs better on lower chlorinated PCDD/Fs than that of -based. Furthermore, possible sources of mismatch between measured and predicted values in winter (3–7 °C) were discussed. Gas adsorption artifact was demonstrated to be of minor importance for the phenomena observed. On the other hand, large deviations of slopes (m_r) and intercepts (b_r) in logK_p vs. plots from theoretical values are observed in the literature data and these are found to be linearly correlated with ambient temperatures (P<0.001) in this study. This indicates that the non-equilibrium partitioning of PCDD/Fs in winter may be significantly influenced by the colder temperatures that may have slowed down the exchange between gaseous and particulate fractions.     

土壤中多环芳烃的SPMD辅助解吸行为研究

为了开发一种表征土壤中憎水性有机污染物解吸及生物有效性的新方法,建立了半透膜被动采样装置（SPMD）研究土壤中有机污染物解吸行为的方法,利用SPMD分析了多环芳烃菲、芘和苯并［a］芘在3种不同性质土壤中的辅助解吸行为.结果表明,SPMD是一种很好地表征土壤中憎水性有机污染物解吸及生物有效性的手段. SPMD辅助解吸多环芳烃的效率与土壤有机质及多环芳烃性质有关.随着土壤有机质含量的降低,土壤中菲和芘的SPMD解吸率逐渐升高,对于10 mg/kg染毒水平,当土壤有机质含量由18.68%降低到0.3%时,2种化合物的解吸率分别由56.45%和48.28%上升到接近100%;但是对于苯并［a］芘,粘土表现出明显的滞留能力,在有机质含量（0.3%）很低、粘土含量（39.05%）较高的3号土壤中,苯并［a］芘的解吸率仅有66.97%.不同多环芳烃SPMD辅助解吸率差别很大,随着土壤有机质含量的降低,以及污染物浓度的提高,菲和芘的解吸差异逐渐缩小,而苯并［a］芘与上述2种多环芳烃的差异很大,主要是由于苯并［a］芘具有高度亲脂性,并且分子较大,造成其容易滞留在粘土的微孔及有机质的致密结构中.     

苯并芘对稀有鮈鲫的内分泌干扰效应研究

为评价典型有机污染物对长江三峡库区上游特有珍稀鱼类的环境风险,本实验以稀有鮈鲫为对象,研究了低剂量多环芳烃(PAHs)暴露而引起的内分泌干扰效应.将成年稀有鮈鲫暴露于不同浓度(0、0.1、0.3、1.0和3.0μg·L-1)的苯并芘(Ba P)中28 d,测定了体质系数、性激素含量、下丘脑-垂体-性腺(HPG)轴和肝脏中与繁殖相关基因的表达.结果显示:在雌鱼中,Ba P暴露后,睾酮(T)的含量显著升高,雌二醇(E2)的水平显著下降并改变了T/E2的比值;在雄鱼中,T和E2的含量都显著下降.雌雄鱼性激素的改变可能与类固醇合成相关基因(Cyp17、Cyp19a)表达量的改变有关.Ba P暴露显著抑制了雌雄鱼肝脏中卵黄蛋白原(VTG)基因的表达.以上检测到的激素或者基因表达的改变主要发生在高剂量(3.0μg·L-1)Ba P暴露下,而长江上游库区水体中多环芳烃含量较低(100 ng·L-1),因此推测,库区存在的多环芳烃不会对三峡库区上游水体中的鱼类产生内分泌干扰效应.     

光助Fenton反应降解水溶性染料曙红Y脱色研究

对水溶性染料曙红Y使用Fenton试剂结合光催化氧化降解褪色的过程进行了研究,对该反应的4种主要影响因素加以分析:染料浓度、Fenton试剂用量、光源、初始pH值。经过系列的研究分析得出了曙红Y降解的最佳降解条件,并对Fenton试剂光催化氧化反应机理进行了初步探讨。实验结果表明:太阳光照射能有效地促进曙红Y的降解褪色(脱色率大于95%),明显缩短褪色时间,节约氧化剂的用量。当Fe2+浓度在3.50×10-5~7.19×10-5mol/L之间以及H2O2的摩尔量为染料摩尔量的50~100倍时,太阳光光照能有效地促进0.10 g/L以下浓度的曙红Y的降解。     

Fenton试剂催化氧化降解微囊藻毒素的动力学研究

针对饮用水中藻毒素污染的问题,以微囊藻毒素作为研究对象,系统地研究了Fenton试剂催化氧化降解微囊藻毒素的效能,并对其催化氧化微囊藻毒素过程的反应动力学进行了探讨。实验结果表明,Fenton试剂对微囊藻毒素具有较好的催化氧化效果,当[H2O2]=8 g/L、[Fe2 ]/[H2O2]=1/12、pH=2时,反应在30 min内微囊藻毒素的去除率可达90%以上。同时通过实验得出了Fenton试剂催化氧化降解微囊藻毒素的动力学方程为:r=2.31×106exp[-23 300/(RT)]C0.H492O2C2.22M。