天然斜发沸石对氨氮的快速吸附特性研究

通过静态摇床试验研究了天然斜发沸石对氨氮的吸附特性,以及沸石投加量和外加金属阳离子对其快速吸附氨氮特性的影响。结果表明,沸石对氨氮的等温吸附过程更符合Langmuir吸附模型,其最大吸附量为12.903mgg;沸石粒径减小,有利于沸石对氨氮的交换吸附,不同粒径沸石对氨氮的吸附均符合准二级动力学过程;斜发沸石中与氨氮进行离子交换的阳离子主要为Na+,其次为Ca2+,随着吸附氨氮浓度的升高或吸附时间的延长,Na+与NH4+吸附去除量的比值呈下降趋势,而Ca2+的比值呈上升趋势。沸石投加量与氨氮去除率和沸石释放至水中的总金属阳离子浓度成正比,随着投加量增加Na+与NH4+吸附去除量的比值由1.222增至1.383;溶液中分别加入40mgL的K+,Na+,Ca2+,Mg2+4种离子,对沸石吸附氨氮产生抑制作用的强弱顺序为K+Ca2+Na+Mg2+。     

pH和共存阳离子对草莓茎吸附水体氨氮的影响

为了开发新型氨氮吸附剂和探讨环境因素对氨氮吸附的影响,以草莓茎为吸附材料,通过批平衡法研究了不同初始pH、共存阳离子、初始浓度和温度下氨氮去除的特点.结果表明,等温吸附符合Langmuir和Freundlich这2种模型,理论最大吸附量qm在15、25和35℃下分别为3.05、4.24和4.79 mg.g-1.温度升高有利于草莓茎对氨氮的吸附.草莓茎吸附氨氮最适初始pH为4～8.低pH减少草莓茎表面负电荷,高pH减少溶液中NH 4+的含量,都减少氨氮的吸附.草莓茎对溶液pH的缓冲则缓和了两者对氨氮吸附的影响.共存阳离子K+、Na+、Ca2+、Mg2+对草莓吸附铵离子没有竞争作用,而Zn2+、Al3+则由于其水解降低溶液的pH而显著降低草莓茎对氨氮的吸附.草莓茎吸附氨氮的应用pH范围较广且不易受废水中常见金属阳离子的干扰,说明草莓茎不仅可以作为废水中氨氮的吸附剂原料,而且较大多数矿物原料还有其自身的优势.     

竞争性阳离子对粉煤灰合成沸石除氨氮的影响

研究了四种竞争性阳离子(K+、Na+、Ca2+、Mg2+)对三种改性粉煤灰合成沸石(Na沸石,Ca沸石,Al沸石)除氨氮能力的影响,并测定了合成沸石对四个湖泊水样(太湖、巢湖、洱海、抚仙湖)中氨氮的去除效果。结果表明,与Na+、Ca2+、Mg2+比较,K+对合成沸石除氨氮影响大得多;而前三者的影响大小的顺序为Na+Ca2+Mg2+。在纯水中,或不同竞争性阳离子存在下,或天然湖泊水样中,Al沸石和Ca沸石对氨氮的去除能力均远高于Na沸石。太湖和巢湖主要含Na+和Ca2+;洱海水样主要含Ca2+;抚仙湖水样主要含Ca2+和Mg2+;但四个湖泊水样中K+的浓度均为最低。Al沸石和Ca沸石对四个天然湖泊水样中的氨氮具有良好的去除效果,去除率达77%～90%。     

贵州典型森林群落植被冠层的酸雨淋溶特征及缓冲作用

在贵州龙里地区开展酸雨模拟实验,并进行天然降雨连续监测,采集马尾松、灌丛冠层穿透雨,结果表明:①研究区降雨中主要阳离子浓度依次为NH4+Ca2+K+Na+Mg2+,降雨pH值大于6.0时,降雨中NH4+含量降低,Ca2+占优势;降雨中主要阴离子浓度依次为SO42-NO3-Cl-;冠层穿透雨与降雨相比,Na+、K+、Ca2+、Mg2+、Cl-、NO3-、SO42-和有机酸富集,特别是K+、Ca2+、SO42-和有机酸富集倍数最大.②森林冠层对酸雨的缓冲作用体现在酸雨中H+与树叶组织中的盐基阳离子发生交换反应,淋出K+、Mg2+、Ca2+等阳离子,减少了酸雨中H+含量.Na+相对惰性,在降雨和穿透雨中的含量变化不大;K+、Mg2+、Ca2+的淋出是冠层缓冲降雨酸度的主要原因,其中K+和Ca2+作用最突出,其次是Mg2+.③贵州典型森林群落植被冠层的缓冲作用随降雨pH值而变化.对pH值接近3.0的强酸性降雨,经过冠层形成的穿透雨pH值大于降雨,典型森林群落植被冠层对酸雨的缓冲作用依次为马尾松林针阔混交林灌丛;对4.0pH6.0的降雨,马尾松林冠层使降雨更加酸化,典型森林群落植被冠层对酸雨的缓冲作用依次为针阔混交林灌丛马尾松林;对pH值大于6.0的非酸性降雨,经过冠层后被酸化,穿透雨pH值小于降雨;穿透雨pH值基本在4.0～6.0范围内.     

牛粪生物炭对水中氨氮的吸附特性

以牛粪生物炭为吸附剂,研究了p H、粒径、投加量、温度和共存阳离子等因素对牛粪生物炭吸附氨氮的影响及吸附特性.结果表明,共存阳离子Na+、Ca2+的存在对牛粪生物炭吸附氨氮有抑制作用,在Na+、Ca2+浓度相同条件下对氨氮吸附影响大小顺序为Na+Ca2+;牛粪生物炭吸附氨氮的最佳初始p H值应在5~8范围;通过对动力学数据进行分析,发现准二级动力学方程(R2=0.967 3)比准一级动力学方程(R2=0.765 9)和Elovich方程(R2=0.724 9)能更好地拟合动力学数据,颗粒内扩散方程拟合结果发现牛粪生物炭对氨氮的吸附包括表面吸附和颗粒内扩散两个过程.吸附等温线拟合发现Freundlich方程(R2=0.976 2)能很好地描述氨氮在牛粪生物炭上的吸附行为.吉布斯自由能变化(ΔGθ)、焓变(ΔHθ)和熵变(ΔSθ)的计算结果表明,牛粪生物炭对氨氮的吸附是自发的吸热过程.     

pH值和离子对诺氟沙星在胡敏酸上吸附特征的影响

根据OECD Guideline 106批平衡实验,研究了pH值、Ca2+浓度和离子类型对诺氟沙星在胡敏酸上吸附特征的影响.结果表明,吸附系数(Kd)随着pH值的增大有先增加后减小的趋势,在pH 4.0和pH 6.0时吸附系数较大.红外光谱表明,pH 3.0有利于诺氟沙星和胡敏酸形成氢键; pH6.0和7.0时胡敏酸的羧基可能与诺氟沙星的氨基形成了肽键.诺氟沙星在胡敏酸上的吸附量和Kd值随着溶液中Ca2+离子浓度的增加而逐渐减小,表明两者之间存在阳离子吸附和竞争吸附.不同类型的阳离子和阴离子的加入都能导致诺氟沙星在胡敏酸的吸附特性存在差异.阳离子的影响趋势主要为价态的影响,即价态越高,在胡敏酸表面吸附位点的吸附能力就越强,对诺氟沙星吸附阻碍作用越显著,表现在诺氟沙星的最大吸附量(Qm)为:M+ (Na+、K+、NH4+) >M2+ (Mg2+、Ca2+、Zn2+);其次受阳离子的离子半径和水解作用的影响.而只有能水解的阴离子才能对诺氟沙星在胡敏酸上的吸附产生明显的阻碍作用.     

深海适冷菌Pseudoalteromonas sp.SM9913胞外多糖对Pb~(2+)和Cu~(2+)的吸附性能研究

采用深海适冷菌Pseudoalteromonas sp. SM9913分泌的胞外多糖(EPS)分别对Pb2+和Cu2+进行吸附,研究了多糖用量、pH、吸附时间和共存离子对EPS吸附性能的影响及EPS对Pb2+和Cu2+的吸附热力学.结果表明,EPS对Pb2+和Cu2+的吸附量随EPS投加量的增加而减小.EPS对Pb2+和Cu2+的最佳吸附pH分别为4.5～5.5和4.5～6.0. EPS对Cu2+的吸附平衡时间为90 min,对Pb2+的吸附平衡时间则长达180 min.共存离子Ca2+、Mg2+、Na+、K+的加入均降低了EPS对Pb2+的吸附量,Ca2+、Mg2+的加入降低了EPS对Cu2+的吸附量,但低浓度的Na+和实验范围浓度的K+不仅没有降低反而增加了EPS对Cu2+的吸附量.Freundlich和Dubinin-Radushkevich方程均能较好地描述SM9913胞外多糖吸附Pb2+和Cu2+的热力学过程,由Dubinin-Radushkevich方程得到SM9913胞外多糖对Pb2+和Cu2+的最大吸附量分别为243.3 mg/g (10℃) 和36.7 mg/g (40℃).胞外多糖吸附金属离子前后的红外光谱分析表明,多聚糖中C-O-C、乙酰基和羟基是起主要吸附作用的官能团.     

天然沸石对氨氮的动态去除过程研究

针对天然沸石去除氨氮的动态过程问题,通过动力学实验、等温吸附实验、共存阳离子实验和阳离子交换实验展开研究。结果显示:沸石对NH+4的吸附过程与准二级动力学模型拟合良好,但在反应初期更符合粒子内扩散模型;沸石对NH+4的吸附等温线符合Langmuir方程;共存阳离子与NH+4存在竞争吸附,其中Ca2+和K+的影响最大;阳离子交换是沸石吸附氨氮的主要方式,并且在反应初期存在不等量交换现象。     

粉煤灰提铝中间产物合成4A分子筛对氨氮的吸附行为研究

采用粉煤灰提铝中间产物合成4A分子筛,利用XRD、SEM、热重分析、化学成分分析、阳离子交换容量对4A分子筛进行表征.考察吸附时间、pH、分子筛投加量、氨氮初始浓度、共存阳离子对其吸附性能的影响,研究其对模拟废水中氨氮的吸附效果,并结合准二级动力学方程、吸附等温线研究吸附性能和机理.结果表明,初始浓度为50 mg·L~(-1)、4A分子筛投加量为5 g·L~(-1)、pH值为6~9、吸附时间为80 min时氨氮去除率可达71.34%;随着氨氮初始浓度升高,其去除率降低,吸附容量增加;共存阳离子Na~+、K~+、Ca~(2+)对NH_4~+有强烈的竞争吸附,Mg~(2+)无明显竞争作用.吸附过程符合准二级动力学方程和Freundlich模型.Langmuir吸附等温线显示最大吸附容量为20 mg·g~(-1).     

酿酒酵母与Ag+的相互作用机制研究

为探讨酿酒酵母与Ag+的相互作用机制,分析了酵母吸附Ag+过程中细胞阳离子的释放状况,并利用红外光谱(FTIR)、带能谱仪的扫描电镜(SEM-EDX)、带能谱仪的透射电镜(TEM.EDx)等手段表征了酵母细胞在吸附Ag+前后表面官能团的变化以及Ag+在酵母细胞中的存在位置和状态.结果表明,酵母细胞吸附Ag+伴随着大量细胞阳离子K+、Na+、Mg2+、Ca2+的释放.Ag+的存在会抑制体系pH值增加,并促进Mg2+、Ca2+的释放.与Ag+的吸附类似,K+、Na+、Mg2+、Ca2+的释放也很快,并且符合准二级动力学方程.酵母对Ag+的吸附,可被认为是离子交换机制和共价结合机制共同发挥作用FTIR证明酵母表面羧基对Ag+的吸附发挥重要作用.电镜分析结果表明,酵母细胞表面不仅吸附了Ag+,同时产牛更高浓度的含Ag沉淀物,使Ag+从溶液中去除,这些含Ag沉淀不均匀地分布于细胞表面,含Ag沉淀的性质以及形成过程还需要借助其他分析手段进行进一步确认.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

ＲｅｍｏｖａｌｏｆｈｅａｖｙｍｅｔａｌｓｆｒｏｍｓｅｗａｇｅｓｌｕｄｇｅｂｙｌｏｗｃｏｓｔｉｎｇｃｈｅｍｉｃａｌｍｅｔｈｏｄａｎｄｒｅｃｙｃｌｉｎｇｉｎａｇｒｉｃｕｌｔｕｒｅＷｕＱｉｔａｎｇ，ＮｙｉｒａｎｄｅｇｅＰａｓｃａｓｉｅ，ＭｏＣｅｈｕｉＦ...     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.