硝酸盐在层状氢氧化镁铝及其焙烧产物上的吸附特性比较

通过静态吸附实验,对比研究了水溶液中硝酸盐在自制层状氢氧化镁铝(每批500 kg)(Mg-Al LDH)及其焙烧产物(Mg-Al CLDH)上的吸附性能和机理, 用多晶X射线衍射对层状氢氧化镁铝(吸附前后)及其焙烧产物(吸附前后)的结构进行了表征.结果表明,硝酸盐在层状氢氧化镁铝及其焙烧产物上的吸附分别是通过离子交换和"结构记忆"效应实现的.硝酸盐在层状氢氧化镁铝及其焙烧产物上的吸附量受吸附时间、温度、吸附剂用量、初始pH值、溶液初始浓度、离子强度等因素的影响.在25～80 ℃的条件下,硝酸盐在层状氢氧化镁铝及其焙烧产物上的吸附均符合Freundlich线性吸附等温方程式.在层状氢氧化镁铝上的吸附为放热反应,平衡吸附量为34.87～26.95 mg·g-1,而在焙烧层状氢氧化镁铝上的吸附为吸热反应,平衡吸附量为45.41～203.44 mg·g-1.焙烧层状氢氧化镁铝可有效脱除溶液中的硝酸盐,吸附后产物在700℃下重复再生3次,吸附量无变化.溶液初始浓度为500 mg·L-1、吸附剂用量为0.1 g、吸附时间为15min、温度为40 ℃是焙烧层状氢氧化镁铝吸附的最佳条件.     

有机改性镁铝层状氢氧化物对酸性橙Ⅱ的吸附研究

采用共沉淀法合成以十二烷基硫酸根为层间阴离子的有机改性镁铝层状双金属氢氧化物(LDHs-SDS),对其进行XRD、FT-IR表征,并研究其对水中阴离子染料酸性橙Ⅱ的吸附特性,探讨了吸附剂投加量、初始pH值、染料浓度、温度、吸附时间等因素对酸性橙Ⅱ吸附性能的影响.结果表明,LDHs-SDS对酸性橙Ⅱ染料废水具有明显的脱色效果,25℃下,0.2 g·L-1和0.4 g·L-1的LDHs-SDS对浓度为100 mg·L-1和200mg·L-1染料的脱色率可分别达到97.41％和97.13％.在pH为3～11之间,吸附效果良好;吸附在2h内完成;LDHs-SDS对酸性橙Ⅱ的饱和吸附量为486.44 mg·g-1.吸附规律较好地符合Langmuir吸附等温方程,吸附反应为吸热反应,且吸附过程符合拟二级反应动力学方程.在阴离子染料去除方面,LDHs-SDS显示出较好的应用前景.     

酿酒酵母吸附Zn2+、Pb(2+)、Ag+、Cu2+的动力学特性研究

利用静态摇瓶实验方法,研究了工业废弃酿酒酵母无缓冲溶液体系吸附Zn2 、Pb2 、Ag 、Cu2 的动力学特性.结果表明,酵母吸附Zn2 、Pb2 、Ag 、Cu2 的动力学过程可以用准二级动力学方程进行描述.金属离子初始浓度在0.08～3.0 mmol·L-1范围内,Langmuir方程可以较好地描述Zn、Pb、Ag的等温吸附行为,Zn、Pb、Ag的理论饱和吸附量分别为0.522 mmol·g-1(34.11 mg·g-1)、0.577 mmol·g-1(119.50mg·g-1)和0.329 mmol·g-1(35.50 mg·g-1).以mol为基础的金属离子吸附量顺序是:Pb＞Zn＞Ag;以mg为基础的金属离子吸附量顺序是:Pb＞Ag＞Zn.Freundlich方程对整个浓度范围内的平衡数据拟合效果较差,但是它可以较好地描述低浓度Zn2 (初始浓度0.08～0.5mmol·L-1)、低浓度Pb2 (0.08～1.0 mmol·L-1)以及高浓度Ag (1.5～3.0 mmol·L-1)的等温吸附行为.酵母吸附Zn2 、Pb2 、Ag 、Cu2 过程中,溶液pH值有不同程度的增加,增加幅度大小顺序是Zn＞Pb＞Ag＞Cu,这间接反映出Zn2 、Pb2 、Ag 、Cu2 与水溶液中H 的竞争力逐步减弱.吸附过程中酵母释放大量的K ,其次是Mg2 ,而Ca2 、Na 的释放量较低,数量级一般可分别达到几百μmol·g-1 、几十μmol·g-1、几到几十μmol·g-1、十几μmol·g-1.     

腐殖酸对生物炭去除水中Cr(Ⅵ)的影响机制研究

以污泥生物炭作吸附剂处理水中Cr(Ⅵ),研究了共存腐殖酸对生物炭吸附性能影响.结果表明,腐殖酸能显著促进生物炭对Cr(Ⅵ)的吸附,大幅提高吸附量以及缩短吸附平衡时间,生物炭吸附过程符合准二级动力学模型.在溶液初始pH4.0,生物炭浓度20 g·L-1,Cr(Ⅵ)初始浓度在50～800 mg·L-1范围下,Langmuir模型比Freundlich模型更好地描述等温吸附行为.加入腐殖酸(20 mg·L-1)后拟合得到的理论饱和吸附量达10.10 mg·g-1,较未加入腐殖酸的吸附量5.56 mg·g-1提高近1倍.在pH 2.0～8.0范围内,吸附量随溶液初始pH值升高而减小.腐殖酸浓度上升,生物炭吸附能力进一步提高.红外光谱显示,生物炭表面的羟基、羧基、酯基、芳香环上C—H和环状结构上的CC等化学活性官能团与Cr(Ⅵ)的吸附有关.结合XPS分析结果,推断腐殖酸共存促进生物炭吸附的机制是:腐殖酸提高了Cr(Ⅵ)在生物炭表面聚集浓度,有利于生物炭对Cr(Ⅵ)的直接吸附和还原,而腐殖酸本身具有的吸附能力增加了对溶液中Cr(Ⅵ)和Cr(Ⅲ)的去除.     

颗粒活性炭对水中邻苯二甲酸二甲酯的吸附特性

研究了颗粒活性炭(GAC)对水中邻苯二甲酸二甲酯(DMP)的静态与动态吸附特性.结果表明,Freundlich和Langmuir等温线模型可以较好的拟合GAC对DMP的吸附.GAC对DMP的吸附容量较大,溶液初始浓度为200mg/L时,GAC对DMP的动态和最大静态吸附容量分别为484.60,450.89mg/g.考察了不同流速条件下(0.65～4.00mL/min)GAC吸附DMP的穿透特性,Yoon-Nelson模型能很好地拟合DMP在GAC柱中的穿透曲线,根据试验数据和Yoon-Nelson模型计算出穿透参数K′、T和穿透点t1以及平衡点t2.在建立了进水流量与Yoon-Nelson穿透模型的参数之间的关系基础上,得到了活性炭柱出水浓度与进水流量和穿透时间之间的动态关系模型.     

紫色土对硫丹的吸附与解吸特征

为揭示硫丹在紫色土中的残留过程、保护土壤生态环境,采用静态吸附和解吸实验,研究了紫色土对硫丹的吸附与解吸特征,考察了温度、吸附剂用量和吸附液初始p H等因素对吸附量的影响.结果表明紫色土对硫丹的吸附动力学过程可以用二级动力学方程很好地描述,获得α-,β-硫丹的初始吸附速率常数分别为0.157 mg·(g·min)-1和0.115 mg·(g·min)-1;吸附热力学过程可以用Langmuir等温吸附模型很好地描述,获得α-,β-硫丹的最大吸附量分别为0.257 mg·g-1和0.155mg·g-1,紫色土吸附硫丹是放热的物理化学过程,但以物理吸附为主.在本研究所设条件下,吸附液初始p H对吸附量的影响较大,温度和吸附剂用量的影响相对较小.解吸实验发现,紫色土吸附的α-,β-硫丹分别在6和4 h时达到最大解吸量(0.029mg·g-1和0.017 mg·g-1),分别占最大吸附量的10.5%和16.1%.     

天然菱铁矿改性及强化除砷研究

我国高砷地下水分布广泛,经济、高效地饮用水除砷技术受到广泛关注.静态批实验采用资源丰富、价格便宜的天然菱铁矿为主要原材料,考虑灼烧温度、时间及添加黏合剂等因素确定最优改性条件使除砷效果达到最佳.结果表明,在加铝量为10 mg.g-1、350℃下恒温灼烧90 min后造粒达到强度要求并除砷效果较优.25℃、固液比为0.5 g∶50 mL、As(Ⅲ)和As(Ⅴ)初始浓度为5 mg.L-1时,吸附后溶液中残留As浓度均<10μg.L-1.静态吸附批实验结果表明,25℃时,接触反应时间为12 h可达到吸附平衡,吸附过程较好地符合Lagergren假二级吸附速率方程;最优改性天然菱铁矿对砷的吸附规律可用Langmuir和Freundlich等温吸附模型很好地描述,As(Ⅲ)、As(Ⅴ)饱和吸附容量分别可以达到1 039、1 026μg.g-1.结合XRD、SEM等研究方法和比表面及孔结构分析初步探讨天然菱铁矿改性以及除砷的主要机制.分析表明,改性后天然菱铁矿比表面积大幅度增大,孔径减小,且在表面活化生成一层圆球状的含Fe(Ⅱ)和Fe(Ⅲ)的化合物.改性天然菱铁矿是一种值得进一步研究并实际应用的除砷材料.     

改性花生壳对水中镉的动态吸附研究

采用高锰酸钾改性花生壳吸附剂对镉离子进行固定床吸附实验,考察了床层高度(30～50 cm)、初始离子浓度(0.55～11.00 mg.L-1)、进料流速(15.11～37.00 mL.min-1)等操作参数对镉吸附特性的影响,同时对吸附穿透曲线进行拟合.实验结果表明,改性花生壳固定床对水中镉具有较好的吸附效果,在吸附操作初期,吸附柱出水镉离子浓度几乎为0(<0.001mg.L-1),吸附操作时间根据不同的操作条件可达2～62 h,镉离子总去除率均大于54%.传质区长度主要受初始离子浓度、进料流速影响.床层高度的增加使得穿透时间增加,但传质区长度几乎保持不变;初始离子浓度和进料流速增加,穿透时间缩短,传质区长度增加.在低浓度条件下,BDST模型实验穿透曲线拟合效果较好(R2>0.99),运用该模型能准确预测吸附柱的操作时间.     

铜离子和孔雀绿在磷酸酯化改性豆壳上的吸附行为

报道了一种功能基为磷酸羟基的酯化豆壳阳离子吸附剂的固相制备技术,研究了铜离子和孔雀绿在改性豆壳上的吸附行为.采用静态批次试验研究了不同实验参数(pH值、吸附剂用量、吸附质浓度和吸附时间)对铜和染料吸附的影响.铜离子和孔雀绿分别在pH≥3.0和6.0时达到最大吸附值.对于浓度为100 mg·L-1的铜溶液,5.0 g·L-1及以上的改性豆壳能去除91%以上的铜;改性豆壳用量≥2.0 g·L-1时,能去除浓度为250 mg·L-1的溶液中95%以上的孔雀绿.改性豆壳对铜离子和孔雀绿的吸附符合Langmuir吸附等温线模型,最大吸附能力分别为31.55 mg·g-1和178.57 mg·g-1.对铜离子和孔雀绿的吸附分别在75 min和7 h达到吸附平衡,准一级反应动力学方程和准二级反应动力学方程能分别描述铜离子和孔雀绿在改性豆壳上的吸附过程.     

壳聚糖季铵盐磁性颗粒的制备及其对甲基橙的吸附效果

首先在甘氨酸盐酸盐离子液体([Gly]Cl)水溶液中制备了不同取代度的壳聚糖季铵盐,采用共沉淀法制备了纳米Fe3O4.进而以Fe3O4为核,戊二醛作交联剂,通过反相悬浮法制备交联壳聚糖季铵盐磁性颗粒,考察了反应条件对吸附效果的影响.并采用静态吸附法研究了磁性颗粒对甲基橙(MO)的吸附效果.结果表明,在25℃,pH=3的条件下,甲基橙初始浓度从20 mg.L-1增加到150 mg.L-1时,平衡吸附量从37.45 mg.g-1增加到277.5 mg.g-1.运用相关数学模型拟合实验数据得出,该吸附符合Freundlich模型,吸附动力学符合拟二级动力学模型.经4次重复使用后磁性颗粒对甲基橙的吸附率仍高于90%.     

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.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

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.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.