超声波-芬顿法协同降解亚甲基蓝的研究

以亚甲基蓝溶液为模型污染物,在超声波芬顿法协同作用下对亚甲基蓝染料废水的降解作用进行了研究,考察了反应时间、H2O2用量、溶液pH值、Fe^2＋的浓度等因素对亚甲基蓝溶液降解的影响。结果表明,超声波单独降解亚甲基蓝溶液脱色效果不明显,超声波协同H2O2降解亚甲基蓝,加入30%H2O26mL,脱色率约45.80%;溶液pH2.80,Fe^2＋浓度为30mmol/L时,超声波芬顿法协同降解甲基蓝180min,脱色率达92.70%。试验证明,超声波芬顿法是一种降解亚甲基蓝的有效方法。     

天然锰钾矿处理印染废水实验研究

利用天然锰钾矿处理印染废水，讨论了介质pH值、样品用量、样品粒径、反应时间、光照和同存电解质等实验条件对活性艳红X—3B印染废水脱色速率的影响。处理了工业中常用的10种活性染料印染废水和华丰印染厂实际废水，大部分染料的脱色率达到了95％，处理后的华丰印染厂的CODcr和色度都达到了纺织染整工业废水排放一级标准，且天然锰钾矿可以被重复使用。锰的溶解情况研究结果表明，加入染料后，溶液中Mn(Ⅱ)的浓度大大提高，表明染料能将Mn(Ⅳ)还原为可溶的Mn(Ⅱ)，即染料与锰钾矿颗粒物界面发生了氧化还原反应，使染料的发色基团破坏而导致脱色。     

软锰矿对酸性大红GR的氧化脱色研究

本文主要研究了天然软锰矿对酸性大红GR的脱色效果,并从溶液的pH值和软锰矿的用量、粒径以及水浴温度、振荡速度方面探讨了软锰矿对其脱色效果的影响。实验表明,软锰矿可使250mL浓度为40mg/L的酸性大红溶液脱色达到95%以上,脱色效果较好,溶液pH值是影响酸性大红脱色的最主要因素,软锰矿的用量、粒径以及水浴温度、振荡速度对酸性大红脱色影响不大。软锰矿对酸性大红的高脱色率以及红外光谱分析和COD去除率表明,酸性大红在矿物界面发生了氧化还原反应,其显色基团被氧化破坏,但并不能将染料溶液全部氧化去除。软锰矿对酸性大红GR的氧化脱…     

膨润土基多孔材料在染液脱色处理中的应用

本文研制了成型化的膨润土基多孔粘土材料，应用于染液废水的脱色处理。初步探讨了该材料对染料阳离子红X－GRL、直接大红FαG和次甲基蓝的脱色作用及其影响因素。结果表明，该多孔材料对染液具有良好的脱色效果，用于染料阳离子红X－GRL的脱色可以多次再生循环使用。     

Fe/Al交联改性膨润土(MB)对偶氮染料的脱色研究

以铁铝双金属离子低聚物为交联剂,制备了Fe/Al交联改性膨润土(MB),用于处理含偶氮染料的废水。通过改变吸附时间、pH和甲基橙废水浓度及掺加共存无机阴离子等因素,研究了MB对甲基橙的脱色效果。结果表明,改性后的膨润土吸附能力显著增强,对甲基橙有较好的吸附脱色性能。当材料用量0.0200 g,处理甲基橙废水20 mL,废水pH值小于4,处理时间2 h,甲基橙的脱色率可达95%。其吸附甲基橙的过程符合Fre-undlich等温吸附模式,对甲基橙的最大饱和吸附容量为384 mg/g。我国膨润土储量大、价格低,以Fe/Al交联剂为改性剂对天然膨润土进行了改性,得到的MB材料是一类很好的环境友好型吸附剂。     

H_2O_2增效TiO_2/凹凸棒石光催化体系降解亚甲基蓝

以钛酸四丁酯为前驱体,天然凹凸棒石为载体,采用溶胶凝胶法制备了TiO_2/凹凸棒石复合光催化剂,并用XRD、TEM对其进行表征.以亚甲基蓝染料为模拟污染物,采用300 W汞灯为紫外光源,以光催化实验来评价该催化剂的活性,并研究了H_2O_2的引入对光催化活性的影响.实验结果表明,H_2O_2能显著提高染料的脱色效率:亚甲基蓝的初始浓度为50 mg/L,催化体系为2 mmol/L H_2O_2+0.5 g/L TiO_2/凹凸棒石+UV(紫外线),光催化10 min后其脱色率为95%,相对于单独的0.5 g/L TiO_2/凹凸棒石+UV催化体系,其脱色率提高了约50%.全波段扫描显示,加入H_2O_2后,亚甲基蓝在290 nm对应的苯环吸收蜂急剧下降,665 nm对应的最大吸收峰则近乎消失,且没有新的吸收峰产生.     

Fe-ZSM-5分子筛催化降解染料废水的研究

传统的Fenton均相亚铁盐催化剂处理染料废水,具有难以避免的二次污染和亚铁离子流失问题。分子筛催化剂相比传统催化剂具有高效环保的特点,在催化氧化染料废水领域有着良好的前景。本文通过液相离子交换法制备了Fe-ZSM-5非均相分子筛催化剂,替代传统的亚铁盐催化剂,应用X射线衍射对制备的Fe-ZSM-5分子筛催化剂进行表征,表明随离子交换次数的增加,Fe-ZSM-5催化剂负载的铁量上升,且较好地保持了分子筛结构,有利于提高亚铁离子的催化能力。通过实验确定了Fe-ZSM-5催化剂催化反应的最佳温度、pH值、Fe-ZSM-5的用量、反应时间等工艺参数,比较了Fe-ZSM-5催化剂和传统Fenton均相催化剂降解染料废水的脱色率和废水中铁离子的残留量,结果表明Fe-ZSM-5的脱色率达到98.5%,相比于Fenton均相催化剂的脱色率提升约3%;两种催化剂的铁离子残留量差别显著,Fe-ZSM-5催化剂处理的废水中只产生微量的Fe离子,可以认为Fe-ZSM-5非均相分子筛催化剂有效地解决了催化剂损耗和二次污染问题。     

夏子街膨润土在碱性染料废水处理中的应用研究

以纳基和钙基夏子街膨润土为吸附剂,通过改变吸附时间、吸附剂用量、染料溶液浓度、初始pH值分析其对碱性红46和碱性兰41脱色率的影响,并对其吸附动力学、吸附热力学和吸附机理进行了研究.结果表明,2种膨润土对2种碱性染料废水的最佳脱色条件具有一定差异.准一级动力学模型对膨润土吸附碱性染料废水的过程描述更准确,膨润土对碱性红46的吸附是自发吸热反应,对碱性兰41的吸附是自发放热反应,膨润土对2种碱性染料废水的吸附既有物理吸附也存在离子交换吸附.     

纳米铁还原脱氮动力学及其影响因素

饮用水中硝酸盐(NO3-)对人体健康有危害。为了去除水溶液中NO3-,在实验室制得纳米铁颗粒。它的粒径为20～40 nm,比表面积(BET)为49.16 m2/g。本研究通过批实验考察了纳米铁对NO3-还原脱氮动力学性质和影响NO3-脱氮快慢的主要因素,如反应pH、纳米铁投加量和NO3-起始浓度。实验结果表明,pH越低越有利于NO 3-还原。在一定范围内,NO 3-还原速率随纳米铁投加量增加而增大,而随NO 3-起始浓度升高而降低,反应遵循准一级反应动力学方程,表面吸附和氧化还原反应是纳米铁对NO3-脱氮的主要去除机理。纳米铁对NO3-还原过程中可能反应的途径进行了讨论,NO3-还原产物取决于反应条件。在本研究条件下,纳米铁对NO3-脱氮的最终产物主要为NH4+-N而不是N2,必须进行更多的研究来解决这一问题。     

掺铁-TiO2/膨润土复合光催化材料制备及性能

采用酸性溶胶法制备掺铁-TiO₂/膨润土复合光催化剂,利用XRD﹑IR等测试手段对其进行了表征。通过测试甲基橙溶液的脱色率和COD去除率对复合光催化剂的光催化活性进行了评价。结果表明,该催化剂有较高的催化氧化性能,在太阳光照射下,对pH=4﹑质量浓度为20 mg/L的甲基橙溶液进行降解时,其脱色率可达95%以上,COD去除率可达85%以上。该催化剂在经过200℃焙烧活化2.5 h后可多次重复利用。     

广西岩溶区土壤铁锰结核重金属富集的地质特征

广西岩溶区农田土壤重金属污染形势严峻。该地区土壤含有大量铁锰结核,其主要成分为铁和锰的氧化物,对重金属有着较强的富集作用。铁锰结核伴随着土壤形成过程而产生,也是反映土壤形成过程及成土环境变化的良好载体。研究铁锰结核中重金属的富集特征有助于了解广西岩溶区土壤中重金属元素的富集过程和富集特征。文章对广西柳江和桂平的土壤与其中的铁锰结核进行了成分分析,通过微量元素分析得到铁锰结核对Ni、Cu、Cd、Zn、Pb、Co、Ba、As、Cr等重金属元素的富集特征,通过Ti/Al2O3的比值关系推断了铁锰结核与土壤的物质来源。此外,还对铁锰结核进行了激光共聚焦显微拉曼光谱仪（Laser Microscopic Confocal Raman Spectrometer）、扫描电镜和能谱仪（SEM-EDS）分析。通过铁锰结核内部同心环带状圈层结构及其内部的元素分布周期性变化的特征,推测结核形成机制。铁锰结核的形成固定了大量重金属元素,减轻了土壤重金属污染负担;但如果铁锰结核发生了溶解则会导致Mn及受其控制的部分重金属（Co、Cu、Ni、Ba）重新释放回到土壤,加重重金属污染。     

Microbial decolorization and degradation of crystal violet dye by <Emphasis Type="Italic">Aspergillus niger</Emphasis>

Two fungi were isolated and examined to decolorize crystal violet dye, frequently used as textile dye and in microorganism staining, using basal salt medium under static condition at 30 °C. The more effective fungus gave less dry weight and lower pH indicating that the process was directed toward the decolorization process giving acidic products rather than microbial growth. The effective fungus was identified as Aspergillus niger and was used in the rest of experiments. Increasing the incubation period more than 10 days did not improve the decolorization process, while the best pH was 5.5. The decolorization process was effective (up to 84.6 %) with the examined range of dye concentrations (10–40 ppm). Sucrose content, as a carbon source, more than 1 % did not improve the decolorization process (80.9 %). Using ammonium sulfate as a nitrogen source, instead of sodium nitrate in the original basal medium, lowered the decolorization process, while using corn steep liquor enhanced the biodegradation up to 96.1 %. Although the dye violet color vanishes in acid medium because of decreasing the possibility of extending the benzene chromophore as a result of binding the nitrogen lone pair in the ammonium ion, the UV–Vis spectra and LC–MS–ESI analysis of the bioassay products proved that the decolorization is due to the biodegradation of the dye rather than the resonance factor in acidic medium or biosorption by fungus mycelia.     

Ferromanganese oxide deposits from the Central Pacific Ocean,II. Nodules and associated sediments

Bulk chemical, mineralogical and selective leach analyses have been made on a suite of abyssal ferromanganese nodules and associated sediments from the S.W. equatorial Pacific Ocean. Compositional relations between nodules, sediment oxyhydroxides and nearby ferromanganese encrustations are drawn assuming that the crusts represent purely hydrogenetic ferromanganese material. Crusts, δMnO₂-rich nodules and sediment oxyhydroxides are compositionally similar and distinct from diagenetic todorokitebearing nodules. Compared to Fe-Mn crusts, sediment oxyhydroxides are however slightly enriched, relative to Mn and Ni, in Fe, Cu, Zn, Ti and Al, and depleted in Co and Pb, reflecting processes of non-hydrogenous element supply and diagenesis. δMnO₂ nodules exhibit compositions intermediate between Fe-Mn crusts and sediment oxyhydroxides and thus are considered to accrete oxides from both the water column and associated sediments.Deep ocean vertical element fluxes associated with large organic aggregates, biogenic calcite, silica and soft parts have been calculated for the study area. Fluxes associated with organic aggregates are one to three orders of magnitude greater than those associated with the other phases considered, are in good agreement with element accumulation rates in sediments, and are up to four orders of magnitude greater than element accumulation rates in nodules. Metal release from labile biogenic material in surface sediments can qualitatively explain the differences between the composition of Fe-Mn crusts and sediment oxyhydroxides.Todorokite-rich diagenetic nodules are confined to an eastwards widening equatorial wedge. It is proposed that todorokite precipitates directly from interstitial waters. Since the transition metal chemistry of interstitial waters is controlled dominantly by reactions involving the breakdown of organic carbon, the supply and degradation rate of organic material is a critical factor in the formation of diagenetic nodules. The wide range of (trace metal/Mn) ratios observed in marine todorokite reflects a balance between the release of trace metals from labile biogenic phases and the reductive remobilisation of Mn oxide, both of which are related to the breakdown of organic carbon.     

Improved methods for selective dissolution of Mn oxides: applications for studying trace element associations

The association of rare earth and other trace elements with Fe and Mn oxides was studied in Fe-Mn-nodules from a lateritic soil from Serra do Navio (Northern Brazil). Two improved methods of selective dissolution by hydroxylamine hydrochloride and acidified hydrogen peroxide along with a classical Na–citrate–bicarbonate–dithionite method were used. The two former reagents were used to dissolve Mn oxides without significant dissolution of Fe oxides, and the latter reagent was used to dissolve both Mn and Fe oxides. Soil nodules and matrix were separated by hand. Inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry after fusion with lithium metaborate, and X-ray diffraction were used to determine the elemental and mineralogical composition of the nodules and soil matrix. The latter was composed of kaolinite, gibbsite, goethite, hematite, and quartz. In the nodules, lithiophorite LiAl₂(Mn^IV₂Mn^III)O₆(OH)₆ was detected in addition to the above-mentioned minerals. The presence of hollandite (BaMn₈O₁₆) and/or coronadite (PbMn₈O₁₆) in the nodules is also possible. In comparison to the matrix, the nodules were enriched in Mn, Fe, K, and P, and relatively poor in Si, Al, and Ti. The nodules were also enriched in all trace elements determined. Phosphorus, As and Cr were associated mainly with Fe oxides; Cu, Ni, and V were associated with both Fe and Mn oxides; and Ba, Co, and Pb were associated mainly with Mn oxides. Distribution of rare earth elements indicated a strong positive Ce-anomaly in the nodules, compared to the absence of any anomaly in the matrix. Some of Ce was associated with Mn oxides. The improved methods achieved almost complete release of Mn from the sample without decreasing the selectivity of dissolution, i.e., without dissolving significant amounts of Fe oxides and other minerals, and provided reliable information on associations of trace elements with Mn oxides. These methods are thus proposed to be included in sequential extraction schemes for fractionation of trace elements in soils and sediments.     

煤及其转化产物中重金属形态分布研究

参考Tessier形态分析程序,对煤及其转化产物中的Mn、Mo和Pb的存在形态进行了实验研究,为原煤使用形态转化中的环境效应评价提供参考。结果表明,Mn、Mo和Pb在原煤、煤焦、气化灰、燃煤灰中的形态变化依次为：可交换态、碳酸盐结合态比例下降,铁锰水合氧化物结合态比例上升;各元素的可交换态和碳酸盐结合态含量之和在原煤、气化灰、燃煤灰中依次减少;对原煤和煤焦中的有机态重金属的重复及高提取剂浓度提取是有效的。     

Potential Influence of Ocean Acidification on Deep-Sea Fe–Mn Nodules and Pelagic Clays: An Improved Assessment by Using Artificial Seawater

In order to assess the potential risk of metal release from deep-sea sediments in response to pH decrease in seawater, the mobility of elements from ferromanganese (Fe–Mn) nodules and pelagic clays was examined. Two geochemical reference samples (JMn-1 and JMS-2) were reacted with the pH-controlled artificial seawater (ASW) using a CO₂-induced pH regulation system. Our experiments demonstrated that deep-sea sediments have weak buffer capacities by acid–base dissociation of surface hydroxyl groups on metal oxides/oxyhydroxides and silicate minerals. Element concentrations in the ASW were mainly controlled by elemental speciation in the solid phase and sorption–desorption reaction between the charged solid surface and ion species in the ASW. These results indicated that the release of heavy metals such as Mn, Cu, Zn and Cd should be taken into consideration when assessing the influence of ocean acidification on deep-sea environment.     

Some geochemical controls on Ni and Co concentrations in marine ferromanganese deposits

The uptake of Ni and Co in the hydrous Mn oxide or the amorphous Fe-oxide phases of ferromanganese deposits in the oceans was studied by electron-microprobe analyses of 17 natural manganese nodules and by experiments on desorption-dissolution of these metals from synthetic Fe oxide or Mn oxides and natural nodule material. Ni was found to occur nearly always in the Mn-oxide phases of natural nodules, while Co occurs both in the Mn-oxide and Fe-oxide phases, with a slight preference for the latter. The solubility of Ni and Co (from coprecipitates of these metals with Fe hydroxides after aging) in seawater was found to depend strongly on the crystallinity of the host phase. The adsorption of Co by the synthetic Mn oxides from seawater was higher than that of Ni. The experimentally determined solubility of Ni and Co in seawater from natural nodule material is extremely low and matches the concentration range of these metals in ocean water.     

Response surface methodology mediated optimization of Remazol Orange decolorization in plain distilled water by Pseudomonas aeruginosa BCH

The bacterium Pseudomonas aeruginosa BCH decolorized and degraded the sulphonated azo dye Remazol Orange in plain distilled water. The effects of different parameters, i.e. pH, temperature and cell mass concentration on the biodegradation of dye in aqueous phase was evaluated using response surface methodology. Optimization was carried out using three-level Box–Behnken design. Predicted values were found to be in good agreement with experimental values (R ² 0.9997 and pred R ² 0.9984), which indicated suitability of the employed model and the success of response surface methodology. Optimum dye decolorization was maximized and the favourable conditions were pH 7.43, temperature 29.39 °C and cell mass concentration 2.88 g l^?1, which resulted in 96.01 % decolorization within 5 h. It was validated from the predicted response (97.37 %). According to the analysis of variance results, the proposed model can be used to navigate the design space. 3D plot analysis disclosed the significant interaction between all three tested factors on decolorization process. The combinations of the three variables predicted during response surface methodology were confirmed through confirmatory experiments. Observations indicated that higher cell mass accelerated the decolorization process. Degradation of the dye was verified through high performance liquid chromatography analysis. Phytotoxicity studies carried out with dye and dye metabolites using Phaseolus mungo, Triticum aestivum and Sorghum vulgare indicated the detoxification of dye.     

Dissolution of hausmannite (Mn3O4) in the presence of the trihydroxamate siderophore desferrioxamine B

That microbial siderophores may be mediators of Mn(III) biogeochemistry is suggested by recent studies showing that these well known Fe(III)-chelating ligands form very stable Mn(III) aqueous complexes. In this study, we examine the influence of desferrioxamine B (DFOB), a trihydroxamate siderophore, on the dissolution of hausmannite, a mixed valence Mn(II, III) oxide found in soils and freshwater sediments. Batch dissolution experiments were conducted both in the absence (pH 4-9) and in the presence of 100 μM DFOB (pH 5-9). In the absence of the ligand, there is a sharp decrease in the extent of proton-promoted dissolution above pH 5 and no appreciable dissolution above pH 8. The resulting aqueous Mn²⁺ activities were in good agreement with previous studies, indirectly supporting the accepted two-step mechanism involving the formation of manganite and reprecipitation of hausmannite. Desferrioxamine B enhanced hausmannite dissolution over the entire pH range investigated, both via the formation of a Mn(III) complex and through surface-catalyzed reductive dissolution. Above pH 8, non-reductive ligand-promoted dissolution dominated, whereas below pH 8, dissolution was non-stoichiometric with respect to DFOB. Concurrent proton-promoted, ligand-promoted, reductive, and induced dissolution was observed, with Mn release by either reductive or induced dissolution increasing linearly with decreasing pH. The fast kinetics of the DFOB-promoted dissolution of hausmannite, as compared to iron oxides, suggest that the siderophore-promoted dissolution of Mn(III)-bearing minerals may compete with the siderophore-promoted dissolution of Fe(III)-bearing minerals.     

Deposition of deep-sea manganese nodules

Manganese at equilibrium in seawater occurs dominantly as Mn²⁺ and inorganic complexes at a concentration ratio of about 1:0.72; solubility decreases exponentially with increasing pH or Eh. However, the nodule oxides birnessite and todorokite are at least four orders of magnitude undersaturated relative to the Mn concentrations of seawater, and are metastable relative to hausmannite and manganite. This apparent lack of equilibrium is explicable by the mechanism of precipitation.Surfaces assist Mn precipitation by catalyzing equilibration between dissolved and reactive O₂ and simultaneously also by adsorbing ionic Mn species. The effective Eh at the surface becomes 200–400 mV above that of seawater; the oxidation rate of Mn increases about 10⁸ ×, and the activation energies for Mn oxidation decrease ~ 11.5 kcal/mole. Consequently, marine Mn nodules and crusts form by adsorption and catalytic oxidation of Mn²⁺ and ferrous ions at nucleating surfaces such as sea-floor silicates, oxyhydroxides, carbonates, phosphates and biogenic debris. The resulting ferromanganese surfaces autocatalyze further growth. In addition, Mn-fixing bacteria may also significantly accelerate accretion rates on these surfaces.Mn which accumulates in submarine sediments may be diagenetically recycled in response to steep solubility gradients causing upward migration from more acidic and reducing horizons toward the sea floor. In contrast, the concentrations of the predominant ferric complexes, Fe(OH)₃⁰ and Fe(OH)₄^?, are relatively less sensitive to the Eh's and pH's found in this environment; Fe is therefore not as readily recycled within buried sediments. Consequently, Fe is not so effectively enriched on the sea floor, although it precipitates more readily than Mn because seawater is saturated in amorphous Fe(OH)₃.The metastable, perhaps kinetically-related, Mn oxides of nodules have a characteristic distribution: birnessite predominates in oxidizing environments of low sedimentation rate and todorokite where sedimentation rates and diagenetic Mn mobility are higher. Surface adsorption and cation substitution within the disordered birnessite-todorokite structure account for the high trace element content of Mn nodules.