污泥的热解动力学实验研究

利用热重分析法对扬子污水处理厂的污泥进行了热解动力学实验研究。实验结果表明：在20℃／min的升温速率下,热解过程中有3个失重速率较高的阶段,这3个阶段以挥发分的析出为主。通过Coats--Redfern指数积分法,求解了这3个阶段的化学反应动力学参数——频率因子A和活化能E,最后得到污泥的热解动力学方程。     

造纸污泥热解特性及动力学研究

为了解污泥在氮气氛围下的热解特性,利用热重分析仪对造纸污泥进行了实验研究。实验发现,在10℃/min和20℃/min的升温速率下,污泥热解过程都经历了三个阶段的失重。实验还发现污泥与煤混合物的热解速率在固定碳燃尽阶段与单独污泥热解相比较得到了较大的提高。并根据对热重曲线的分析,得到污泥的反应动力学参数:频率因子和活化能。     

污泥干燥特性及其模型求解

相同质量污泥(3.0±0.01)g在85¹45℃下进行恒温干燥实验,得到污泥干燥过程中含水率、干燥速率等变化规律,采用多元线性回归对实验数据进行分析,得到污泥干燥动力学模型。结果表明:污泥在干燥过程中经历加速、恒速和降速3个阶段,3个阶段的分界点固定在污泥失重率为10%和65%处而不随干燥温度的变化而变化;在同一干燥温度下,饼状污泥的干燥速率大于球状污泥;Logarithmic干燥模型MR=a·exp(-kt)+b在各干燥温度下均最适宜表述污泥干燥过程,其参数a、b与干燥温度T呈二次多项式关系,参数k与干燥温度T呈一次线性关系;饼状污泥的有效扩散系数D eff在9.21×10-6145℃下进行恒温干燥实验,得到污泥干燥过程中含水率、干燥速率等变化规律,采用多元线性回归对实验数据进行分析,得到污泥干燥动力学模型。结果表明:污泥在干燥过程中经历加速、恒速和降速3个阶段,3个阶段的分界点固定在污泥失重率为10%和65%处而不随干燥温度的变化而变化;在同一干燥温度下,饼状污泥的干燥速率大于球状污泥;Logarithmic干燥模型MR=a·exp(-kt)+b在各干燥温度下均最适宜表述污泥干燥过程,其参数a、b与干燥温度T呈二次多项式关系,参数k与干燥温度T呈一次线性关系;饼状污泥的有效扩散系数D eff在9.21×10-6².22×10-5m2/min,球状污泥的有效扩散系数D eff在6.55×10-62.22×10-5m2/min,球状污泥的有效扩散系数D eff在6.55×10-6¹.37×10-5m2/min。且随着干燥温度的上升,有效扩散系数D eff呈上升趋势。在相同干燥温度下,饼状污泥的有效扩散系数大于球状污泥。     

冷冻对脱水污泥干燥与燃烧特性的影响

为了研究冷冻对脱水污泥干燥与燃烧特性的影响,考察了不同冷冻温度对污泥干燥效果的影响.利用同步热重分析仪(TG-DTA)研究了不同冷冻温度和升温速率对脱水污泥燃烧特性的影响,并进行了污泥燃烧动力学分析.结果表明:与原泥相比,冷冻将脱水污泥变成了可进行破碎的硬质结构,当温度降到-20℃时,破碎污泥的干燥速率提升了41.46...     

造纸污泥与褐煤混合燃烧特性及动力学研究

该文通过造纸污泥和褐煤的混合燃烧的热重实验,得到TG和DTG曲线,分析不同混合比例以及不同升温速率(10、20及40 K/min)对燃烧过程的影响,并对燃烧动力学模型的相关参数进行求解,得到了不同燃烧条件下的活化能。研究发现褐煤的燃烧过程有一个明显的失重峰,对应的工况为10 K/min升温速率,其最大失重速率为-7.6%,对应燃烧温度为403.3℃。污泥的燃烧过程分为挥发分和固定碳2个燃烧过程,分别出现在270~575℃和575~727℃之间,采用Coats-Redfern方程计算得到的活化能分别为82.47 kJ/mol和199.26 kJ/mol。污泥与褐煤混合燃烧时,混合试样的最大失重速率随升温速率的提高而增加。通过KAS等转化率及Coats-Redfern方程2种方法分析得出,污泥与褐煤混合燃烧时,污泥的加入可降低混合物着火所需的活化能,降低着火温度,改善燃烧过程。     

颗粒状污泥的干燥特性及表观变化

对3种不同质量等级的污泥颗粒（2.5、5和10 g）在100、200、300、400和500℃下进行恒温干燥实验,通过观察污泥的失重特征和表观形态的变化,深入研究了污泥干燥过程、失重速率的变化规律.结果表明,污泥在100～200℃下的干燥过程分为加速阶段、恒速阶段和降速阶段,而在300～500℃下并没有真正的恒速阶段,...     

不同形状污泥干燥特性的差异性及其成因分析

通过对100~300℃恒速干燥条件下饼状污泥和球状污泥的失重速率、干基质量变化的测定,系统分析了不同形状污泥干燥特性的差异及造成这种差异的原因.结果表明,饼状污泥在干燥过程中会产生裂缝,并分裂成若干小块,而球状污泥仅仅会产生体积收缩,形状并未发生变化.由于表观形态变化的差异,导致了污泥干燥过程的差异,饼状污泥的干燥过程分为升速和降速2个阶段,而球状污泥的干燥过程则分为升速、恒速和降速3个阶段;饼状污泥的平均干燥速率大于球状污泥.在150℃以上干燥时,饼状污泥的有机物在水分蒸发的同时即开始分解,而球状污泥则在水分蒸发完后才开始发生有机物分解.     

Fe-絮凝降阻法处理后的印染污泥燃烧特性

为明确印染污泥焚烧特性,提高其处理效率.以Fe-絮凝降阻法深度处理的印染污泥为研究对象,通过TG-DTG热重曲线法研究不同干燥时间（1.5、2.0、2.5、3.0、3.5和4.0 h）对深度处理的印染污泥燃烧特性的影响,并对深度处理的印染污泥燃烧过程的动力学和失重速率进行拟合.结果表明:不同干燥时间下,深度处理的印染污泥的焚烧过程均可分为4个阶段,阶段1为水蒸发阶段（15.9~106.9℃）,阶段2为低沸点有机物析出阶段（106.9~235.5℃）,阶段3为挥发分的析出和燃烧阶段（235.5~479.0℃）,阶段4为难挥发物质和碳酸盐分解阶段（479.0~852.2℃）,污泥最大失重率均在410.0℃左右,最大失重均出现在阶段3.最佳干燥时间为2.0 h（含水率为3.60%）,该条件下深度处理的印染污泥在阶段3失重峰值前、后分别为0.5级和2级反应,活化能分别为7.227和87.040 kJ/mol.失重峰值前、后的失重速率方程分别为y=9.003 18-0.099 68x（R2=0.998 1）和y=5.576+2.105/{1+exp[（x-18.076）/1.349]}（R2=0.997 8）.研究显示,深度处理的印染污泥主要在第3阶段燃烧,所得失重速率方程与其第3阶段燃烧的失重速率数据较好吻合.      

酸-低热联合处理对剩余污泥脱水性能的影响

为有效降低城市污水处理厂剩余污泥含水率,通过酸-低热（温度 < 100℃）联合处理污泥,探索该方法对污泥的脱水性能.研究不同pH、反应温度、反应时间对污泥脱水性能的影响,并对污泥上清液中SCOD、蛋白质、多糖的浓度以及污泥Zeta电位和污泥形貌进行分析,初步探讨其脱水的作用机理.结果表明:①酸-低热联合处理污泥时,污泥溶解性有机质大量释放,经过40 min反应,上清液中SCOD浓度达到925.76 mg/L,表明该方法能有效破解污泥EPS（胞外聚合物）,释放内部结合水.②原污泥Zeta电位为-14.10 mV,酸-低热联合处理后降至-3.49 mV,污泥颗粒之间的静电斥力显著降低.③酸-低热联合处理有利于污泥的絮凝作用,显微镜观察处理后的污泥絮凝物大且结构紧密,污泥脱水性能得到改善.④试验获得的最佳处理条件为pH 3、温度90℃、加热时间40 min,在该条件下,污泥真空脱水初始速率可达20.67 mL/min（以80 g原泥计）,泥饼真空抽滤后含水率可降至63.05%.研究显示,酸-低热联合处理可有效提高剩余污泥脱水性能,并能释放较多溶解性有机质,抽滤后污泥含水率可降至接近60%,是一种可行的低能耗污泥脱水方法.      

制备工艺对nZVI/污泥基生物炭中Zn、Cu、Pb形态分布及其生态风险的影响

以市政污泥为原料、纳米零价铁（nZVI）为添加剂,采用热解法制备污泥生物炭,考察了nZVI添加量、热解温度和升温速率对生物炭中Zn、Cu、Pb形态分布及其生态风险的影响。结果显示:高nZVI添加量、高热解温度及低升温速率可提高稳定态（BCR法） Zn、Cu和Pb的含量;高nZVI添加量可促使Zn、Cu和Pb向可氧化态转化,而高热解温度和低升温速率有利于残渣态Zn、Cu和Pb的生成;最优nZVI添加量、热解温度和升温速率分别为2000 mg/kg,800℃和4℃/min。此外,当nZVI添加量为800 mg/kg、热解温度为800℃和升温速率为2℃/min时有利于降低Zn、Cu和Pb的生态风险;Zn、Cu和Pb总体生态风险等级分别为低风险、低风险和无风险,与Cu和Pb相比,Zn的生态风险较高;以RI值为评价指标,nZVI/污泥基生物炭的优化制备工艺为:nZVI添加量为200 mg/kg,热解温度为800℃,升温速率为5℃/min。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.