Coordination geometry of Zn~(2+) on hexagonal turbostratic birnessites with different Mn average oxidation states and its stability under acid dissolution

Hexagonal turbostratic birnessite,with the characteristics of high contents of vacancies,varying amounts of structural and adsorbed Mn~(3+),and small particle size,undergoes strong adsorption reactions with trace metal(TM)contaminants.While the interactions of TM,i.e.,Zn~(2+),with birnessite are well understood,the effect of birnessite structural characteristics on the coordination and stability of Zn~(2+)on the mineral surfaces under proton attack is as yet unclear.In the present study,the effects of a series of synthesized hexagonal turbostratic birnessites with different Mn average oxide states(AOSs)on the coordination geometry of adsorbed Zn~(2+)and its stability under acidic conditions were investigated.With decreasing Mn AOS,birnessite exhibits smaller particle sizes and thus larger specific surface area,higher amounts of layer Mn~(3+)and thus longer distances for the first Mn\O and Mn\Mn shells,but a low quantity of available vacancies and thus low adsorption capacity for Zn~(2+).Zn K-edge EXAFS spectroscopy demonstrates that birnessite with low Mn AOS has smaller adsorption capacity but more tetrahedral Zn(~(IV)Zn)complexes on vacancies than octahedral(~(VI)Zn)complexes,and Zn~(2+)is more unstable under acidic conditions than that adsorbed on birnessite with high Mn AOS.High Zn~(2+)loading favors the formation of~(VI)Zn complexes over~(IV)Zn complexes,and the release of Zn~(2+)is faster than at low loading.These results will deepen our understanding of the interaction mechanisms of various TMs with natural birnessites,and the stability and thus the potential toxicity of heavy metal pollutants sequestered by engineered nano-sized metal oxide materials.     

Pretreatment of cyanided tailings by catalytic ozonation with Mn/O

The increasing amount of cyanided tailings produced as a by-product has gained significant attention in recent years because of the rapid development of the gold industry and extensive exploitation of gold mineral resources. The effective use of these secondary resources is becoming an important and urgent problem for all environmental protection staff. Manganese-catalyzed ozonation for the pre-oxidation of cyanided tailings was studied and the effects of Mn^2 + dosage, initial sulfuric acid concentration, ozone volume flow, temperature and agitation speed on pretreatment were examined. The optimum reaction conditions were observed to be: ore pulp density 2.5%, agitation speed 700 r/min, temperature 60°C, Mn^2 + dosage 40 g/L, ozone volume flow 80 L/hr, initial sulfuric acid concentration 1 mol/L, and reaction time 6 hr. Under these conditions, the leaching rate of Fe and weight loss could reach 94.85% and 48.89% respectively. The leaching process of cyanided tailings by Mn^2 +/O³ was analyzed, and it was found that the leaching of pyrite depends on synergetic oxidation by high-valent manganese and O³, in which the former played an important part.     

Mechanism and kinetics of aluminum dissolution during copper sorption by acidity paddy soil in South China

Soil aggregates were prepared from a bulk soil collected from paddy soil in the Taihu Lake region and aluminum (Al) dissolution, solution pH changes during copper (Cu^2 +) sorption were investigated with static sorption and magnetic stirring. Kinetics of Cu^2 + sorption and Al dissolution were also studied by magnetic stirring method. No Al dissolution was observed until Cu^2 + sorption was greater than a certain value, which was 632, 450, 601 and 674 mg/kg for sand, clay, silt, and coarse silt fractions, respectively. Aluminum dissolution increased with increasing Cu^2 + sorption and decreasing solution pH. An amount of dissolved Al showed a significant positive correlation with non-specific sorption of Cu^2 + (R² > 0.97), and it was still good under different pH values (R² > 0.95). Copper sorption significantly decreased solution pH. The magnitude of solution pH decline increased as Cu^2 + sorption and Al dissolution increased. The sand and clay fraction had a less Al dissolution and pH drop due to the higher ferric oxide, Al oxide and organic matter contents. After sorption reaction for half an hour, the Cu^2 + sorption progress reached more than 90% while the Al dissolution progress was only 40%, and lagged behind the Cu^2 + sorption. It indicated that aluminum dissolution is associated with non-specific sorption.     

Relation of lead adsorption on birnessites with di erent average oxidation states of manganese and release of Mn2+/H+/K+

The characteristics of Pb2+ adsorption on the surface of birnessites with di erent average oxidation states (AOS) of Mn, synthesized under acidic and alkali conditions, were investigated. The results indicated that the amount of adsorbed Pb2+ increased with the increase of Mn AOS in birnessites. The amount of Pb2+ adsorbed positively correlated with the amount of released Mn2+, H+, and K+ (r = 0.9962 > 0.6614, n = 14, = 0.01). The released Mn2+, H+, and K+ were derived mostly from the corresponding cations adsorbed on the vacant sites. The maximum amount of adsorbed Pb2+ increased with the increasing vacant cation sites, leading to an increase of the total amount of released Mn2+, H+, and K+, and the increased likelihood for two Pb2+ adsorbed in the region of one side of a vacant site.     

Bio-remediation of acephate–Pb(II) compound contaminants by Bacillus subtilis FZUL-33

Removal of Pb~(2+)and biodegradation of organophosphorus have been both widely investigated respectively. However, bio-remediation of both Pb~(2+)and organophosphorus still remains largely unexplored. Bacillus subtilis FZUL-33, which was isolated from the sediment of a lake, possesses the capability for both biomineralization of Pb~(2+)and biodegradation of acephate. In the present study, both Pb~(2+)and acephate were simultaneously removed via biodegradation and biomineralization in aqueous solutions.Batch experiments were conducted to study the influence of p H, interaction time and Pb~(2+)concentration on the process of removal of Pb2+. At the temperature of 25°C, the maximum removal of Pb~(2+)by B. subtilis FZUL-33 was 381.31 ± 11.46 mg/g under the conditions of p H 5.5, initial Pb~(2+)concentration of 1300 mg/L, and contact time of 10 min. Batch experiments were conducted to study the influence of acephate on removal of Pb~(2+)and the influence of Pb2+on biodegradation of acephate by B. subtilis FZUL-33. In the mixed system of acephate–Pb2+, the results show that biodegradation of acephate by B. subtilis FZUL-33 released PO43+, which promotes mineralization of Pb2+. The process of biodegradation of acephate was affected slightly when the concentration of Pb2+was below 100 mg/L. Based on the results, it can be inferred that the B. subtilis FZUL-33 plays a significant role in bio-remediation of organophosphorus-heavy metal compound contamination.     

Zn(Ⅱ)对生物质碳源处理酸性矿山排水中厌氧微生物活性影响

通过厌氧批实验的方法,探讨了在硫酸盐还原菌(SRB)法处理模拟酸性矿山排水(AMD)的过程中,以油菜秸秆为碳源时,Zn2+浓度对SRB活性的影响.结果表明,在60 d实验中,以油菜秸秆为碳源时,当Zn2+初始浓度在73.7～196.8 mg.L-1范围时,SRB具有良好活性,实验结束时,pH从初始的5.0上升至中性范围,硫酸根还原率达到96%以上,同时Zn2+浓度降至0.05 mg.L-1以下.Tessier固体形态分类、场发射扫描电镜(FE-SEM)和X射线衍射仪(XRD)分析发现,Zn以有机物及硫化物的形态被固定,其中硫化物主要为闪锌矿(ZnS).当Zn2+初始浓度为262.97 mg.L-1时,SRB的活性受到强烈的抑制,实验结束时,pH从初始的5.0降至4.0左右,硫酸根还原率只有27%,Zn2+维持在较高浓度范围(25 mg.L-1).油菜秸秆可以作为SRB法长期处理AMD的缓释碳源,能为微生物生长繁殖提供物质和能量;秸秆的吸附性可降低Zn2+的生物毒性,使得SRB可以适应高浓度的Zn2+;SRB可以通过形成硫化物矿物的形式固定元素Zn.     

Kinetics and mechanism of hexavalent chromium removal by basic oxygen furnace slag

Basic oxygen furnace slag(BOFS) has the potential to remove hexavalent chromium(Cr(VI))from wastewater by a redox process due to the presence of minerals containing Fe2+. The effects of the solution p H, initial Cr(VI) concentration, BOFS dosage, BOFS particle size, and temperature on the removal of Cr(VI) was investigated in detail through batch tests. The chemical and mineral compositions of fresh and reacted BOFS were characterized using scanning electron microscope(SEM) equipped with an energy dispersive spectrometer(EDS)system and X-ray diffractometer(XRD). The results show that Cr(VI) in wastewater can be efficiently removed by Fe2+released from BOFS under appropriate acidic conditions. The removal of Cr(VI) by BOFS significantly depended on the parameters mentioned above. The reaction of Cr(VI) with BOFS followed the pseudo-second-order kinetic model. Fe2+responsible for Cr(VI) removal was primarily derived from the dissolution of Fe O and Fe3O4 in BOFS. When H2SO4 was used to adjust the solution acidity, gypsum(Ca SO4·2H2O)could be formed and become an armoring precipitate layer on the BOFS surface, hindering the release of Fe2+and the removal of Cr(VI). Finally, the main mechanism of Cr(VI) removal by BOFS was described using several consecutive reaction steps.     

Relation of lead adsorption on birnessites with different average oxidation states of manganese and release of Mn^2＋/H^＋/K^＋

The characteristics of Pb2+ adsorption on the surface of birnessites with different average oxidation states (AOS) of Mn, synthesized under acidic and alkali conditions, were investigated. The results indicated that the amount of adsorbed Pb2+ increased with the increase of Mn AOS in birnessites. The amount of Pb2+ adsorbed positively correlated with the amount of released Mn2+, H+, and K+ (r = 0.9962 > 0.6614, n = 14, α = 0.01). The released Mn2+, H+, and K+ were derived mostly from the corresponding catio...     

Effects of chronic and subtoxic chlorobenzenes on adrenocorticotrophic hormone release

Many environmental chemicals and pesticides have been found to alter neuroendocrine communication in exposed biological objects. The environmental loads have primary and secondary effects that can alter the homeostatic regulation potential. Since it is difficult to avoid human exposition, a potentially important area of research to develop in vivo and in vitro experimental models. In this context, the primary aim of this study was to demonstrate the effects of chlorobenzenes on adrenocorticotrophic hormone (ACTH) release. In our experimental study, male Wistar rats were exposed to 0.1, 1.0 and 10 μg/b.w. (body weight) kg of 1,2,4- trichlorobenzene and hexachlorobenzene (ClB) mix via gastric tube for 30, 60 or 90 days. At the endpoints of the experiment blood samples were taken and animals were decapitated. Primary, monolayer adenohypophysis cell cultures were prepared by enzymatic and mechanical digestion. The ACTH hormone content in serum and supernatant media was measured by immuno-chemiluminescence assay. The Mg^2 +-dependent ATPase activity was determined by modified method of Martin and Dotty. Significant differences were detected in the hormone release between the control and treated groups. The hormone release was enhanced characteristically in exposed groups depending upon the dose and duration of exposure. The Mg^2 +-ATPase activity enhanced after chronic and subtoxic ClB exposition. Light microscopy revealed that the adenohypophysis seemed to be more abundant. Results indicate that Wistar rats exposed to subtoxic ClB have direct and indirect effects on hypothalamus–hypophysis–adrenal axis.     

Mg improves biomass production from soybean wastewater using purple non-sulfur bacteria

Soybean wastewater was used to generate biomass resource by use of purple non-sulfur bacteria (PNSB). This study investigated the enhancement of PNSB cell accumulation in wastewater by Mg^2 + under the light-anaerobic condition. Results showed that with the optimal Mg^2 + dosage of 10 mg/L, biomass production was improved by 70% to 3630 mg/L, and biomass yield also was improved by 60%. Chemical Oxygen Demand (COD) removal reached above 86% and hydraulic retention time was shortened from 96 to 72 hr. The mechanism analysis indicated that Mg^2 + could promote the content of bacteriochlorophyll in photosynthesis because Mg^2 + is the bacteriochlorophyll active center, and thus improved adenosine triphosphate (ATP) production. An increase of ATP production enhanced the conversion of organic matter in wastewater into PNSB cell materials (biomass yield) and COD removal, leading to more biomass production. With 10 mg/L Mg^2 +, bacteriochlorophyll content and ATP production were improved by 60% and 33% respectively.     

Effect of AlCl3 concentration on nanoparticle removal by coagulation

In recent years, engineered nanoparticles, as a new group of contaminants emerging in natural water, have been given more attention. In order to understand the behavior of nanoparticles in the conventional water treatment process, three kinds of nanoparticle suspensions, namely multi-walled carbon nanotube-humic acid (MWCNT-HA), multi-walled carbon nanotube-N,N-dimethylformamide (MWCNT-DMF) and nanoTiO₂-humic acid (TiO₂-HA) were employed to investigate their coagulation removal efficiencies with varying aluminum chloride (AlCl₃) concentrations. Results showed that nanoparticle removal rate curves had a reverse “U” shape with increasing concentration of aluminum ion (Al^3 +). More than 90% of nanoparticles could be effectively removed by an appropriate Al^3 + concentration. At higher Al^3 + concentration, nanoparticles would be restabilized. The hydrodynamic particle size of nanoparticles was found to be the crucial factor influencing the effective concentration range (ECR) of Al^3 + for nanoparticle removal. The ECR of Al^3 + followed the order MWCNT-DMF > MWCNT-HA > TiO₂-HA, which is the reverse of the nanoparticle size trend. At a given concentration, smaller nanoparticles carry more surface charges, and thus consume more coagulants for neutralization. Therefore, over-saturation occurred at relatively higher Al^3 + concentration and a wider ECR was obtained. The ECR became broader with increasing pH because of the smaller hydrodynamic particle size of nanoparticles at higher pH values. A high ionic strength of NaCl can also widen the ECR due to its strong potential to compress the electric double layer. It was concluded that it is important to adjust the dose of Al^3 + in the ECR for nanoparticle removal in water treatment.     

低浓度锌及其EDTA配合物长期暴露对鲫鱼肝脏锌富集及抗氧化系统的影响

选择幼龄鲫鱼为材料 ,研究锌(Zn²⁺)及其配合物(Zn-EDTA)低浓度长期暴露(40d)对鲫鱼(Carassius auratus)肝脏锌富集和抗氧化防御系统的影响 .结果表明 ,鲫鱼肝脏中锌的积累量随锌暴露浓度的升高而增加,且Zn²⁺处理明显高于Zn EDTA处理 .2种形态锌对鲫鱼肝脏超氧化物歧化酶 (SOD)、过氧化氢酶 (CAT)和谷胱甘肽过氧化物酶 (GPx)均表现出抑制作用 ,其中Zn²⁺暴露浓度与酶活性之间存在良好的剂量效应关系;Zn²⁺在低浓度时对谷胱甘肽转硫酶(GST)有诱导作用 ,高浓度时为抑制作用 .Zn EDTA对GST活性始终产生抑制作用 .CAT与GPx对锌暴露比GST和SOD更为敏感 ,适合作为水环境锌污染的早期监测指标 .     

复合污染对Pb2+在固定床系统中的动态吸附过程影响及机制

针对复合污染体系对污染物处理效果的影响问题,以限氧裂解法制备的污泥基生物炭（SSB）为吸附剂,探索其在不同污染体系下的吸附性能变化.基于污泥基生物炭构建固定床系统,研究连续流条件下复合污染体系（Zn2+、NH₄+、H₂PO₄-）对Pb2+在固定床动态吸附行为的影响,对比不同体系下系统运行参数的变化.结果表明:①不同复合体系均对SSB的Pb2+吸附效果产生抑制作用,其影响大小为NH₄+ > Zn2+ > H₂PO₄-.而三元/四元复合污染体系中,H₂PO₄-的加入会减弱复杂体系对Pb2+的吸附抑制作用.②固定床系统中,不同复合体系对吸附穿透曲线参数的影响顺序为Pb2+-Zn2+-NH₄+-H₂PO₄- > Pb2+-Zn2+-H₂PO₄- > Pb2+-Zn2+-NH₄+ > Pb2+-NH₄+-H₂PO₄-.③固定床系统动态吸附量（q_d）与传质区长度（H）的变化分析均显示,复合污染体系会降低固定床吸附性能.④数据拟合结果表明,相比于Yoon-Nelson模型,Thomas模型能更好地描述Pb2+在复合体系中的动态吸附过程,但复合污染会限制动态吸附模型的应用,导致模型预测不准确.研究显示,复合污染体系会显著影响吸附剂在连续流状态下的吸附性能,有选择地处理特定污染物可以减少复合污染体系对净化效果的干扰.      

聚羟基铝柱撑硅藻土的制备及其对水溶液中Cu2+、Zn2+的吸附特性

鉴于天然硅藻土因理化构造缺陷而导致的吸附性能局限性和传统物化方法对硅藻土改性效果的有限性,为了显著改善硅藻土的吸附性能,采用聚羟基铝对硅藻土实施了柱撑改性.通过扫描电镜(SEM)、红外光谱(FTIR)、X射线衍射(XRD)分析了硅藻土柱撑前后理化特性的变化,并考察了柱撑前后硅藻土表面性能及其对Cu~(2+)、Zn~(2+)吸附特性的差异.结果表明,硅藻土最佳柱撑条件为n(OH-)/n(Al3+)=2.2、KCl浓度1.8 mol·L~(-1)、Al/土比10 mmol·g~(-1)、反应温度60℃、反应时间24 h、老化温度200℃、老化时间0.5 h.柱撑后,聚羟基铝被成功置入硅藻壳体内部,形成了有效柱体,增大了孔道间距,拓展了吸附反应界面,使微孔表面羟基数量增多,表面活性增强.柱撑前后硅藻土对Cu~(2+)、Zn~(2+)的等温吸附特性均符合Langmuir模型,吸附动力学特性均符合二级动力学模型.柱撑后硅藻土对Cu~(2+)、Zn~(2+)的吸附容量分别达到7.491 mg·g~(-1)、11.312mg·g~(-1),较柱撑前分别提高了32.9%、33.3%,硅藻土吸附性能得到了极大的改善.     

Aeromonas veronii N8不同类型胞外聚合物的性质及其Zn2+吸附特征

以Aeromonas veronii N8为研究对象,对其松散型胞外聚合物(LB-EPS)和紧密型胞外聚合物(TB-EPS)的性质及其吸Zn~(2+)特征进行了研究.结果表明,LB-EPS和TB-EPS具有不同的多糖及蛋白组成比例;与TB-EPS相比,LB-EPS的分子量分布范围较窄,但其平均分子量较大,TBEPS中含有一些LB-EPS不具有的富含芳香族氨基酸的蛋白质,而LB-EPS则含有少量TB-EPS不具有的腐殖酸类物质;1H NMR与XPS分析发现,两种EPS具有相似的结构与元素组成,但各元素在两者中的组成比例并不相同;LB-EPS和TB-EPS具有相似的Zn~(2+)吸附规律,经90 min后二者均能达到吸附平衡,但LB-EPS的吸附率一直大于TB-EPS,二者的吸附率则随着EPS浓度的增加而变大,并随着Zn~(2+)浓度的增加而变小;对比Zn~(2+)吸附前后,两种EPS中属于核酸、多糖与蛋白质在内的一些特征官能团的强度或位置则发生了一定的变化,表明这些特征峰在吸附过程具有不同的功能作用;而LB-EPS和TB-EPS的Zn~(2+)吸附过程则可分别采用Freundlich和Temkin模型进行描述.     

热解条件对生物炭性质和氮、磷吸附性能的影响

以橡木为原料,在不同的热解终温、升温速率和恒温时间下制备生物炭.对生物炭产率、p H、元素组分、工业组分、比表面积、红外光谱等理化特征进行分析,并考察生物炭对水溶液体系中NO-3-N、NH+4-N、PO3-4-P的吸附性能.结果表明:生物炭的产率受热解终温影响最大(极差:54.57%),恒温时间次之(极差:1.16%),升温速率最小(极差:0.42%).随热解终温、升温速率和恒温时间的增加,所得生物炭的p H和C含量增加,而H和O含量降低.热解终温对生物炭表面官能团影响较大,升温速率和恒温时间基本无影响.生物炭对氮、磷的吸附性能主要受热解终温影响.NO-3-N的吸附量最大可达2.80 mg·g-1(600℃),且随热解终温的升高呈指数增加.比表面积、表面碱性官能团和表面金属氧化物与NO-3-N吸附有关.随热解终温的增加,NH+4-N吸附量降低,最大吸附量为3.12 mg·g-1(300℃).阳离子交换量(CEC)是影响NH+4-N吸附的主要因素.PO3-4-P吸附量随热解终温的增加呈先增后减的趋势(在500℃达到最大,为9.75 mg·g-1),且吸附过程主要受生物炭表面碱性官能团和表面金属氧化物的影响.     

磁性生物炭对重金属污染废水处理条件优化及机理

将水稻谷壳经改性和负磁后制得磁性谷壳生物炭(BC-Fe),通过正交实验研究了pH、生物炭添加量、吸附时间和转速对磁性谷壳生物炭吸附实际污染废水中Cd~(2+)和Zn~(2+)的影响,提出了磁性谷壳生物炭作为实际污染废水处理材料的最佳操作条件,并应用于多步骤废水处理系统中,同时进行了BC-Fe的再生吸附实验.正交实验结果表明,在pH为6.0、固液比为6.0 g·L~(-1)、吸附时间为1.0 h、转速为160 r·min~(-1)的条件下,磁性谷壳生物炭对Cd~(2+)和Zn~(2+)的去除率最高,分别达到61.1%和60.4%,吸附量分别为8.6 mg·g~(-1)和21.3 mg·g~(-1).在实验所设条件下,Cd~(2+)和Zn~(2+)的综合去除效果随着pH和生物炭添加量的增加而显著升高,吸附时间和转速的影响未达显著水平.在多步骤废水处理系统中,使用CaO和Na_2S作为前处理,利用磁性谷壳生物炭二次处理,可使实际污染废水中Cd~(2+)、Zn~(2+)、Pb~(2+)、Mn~(2+)、Fe~(2+)的去除率分别达到100%、99.8%、99.3%、97.8%、100%,SS降为1.0 mg·L~(-1),此时系统pH为7.5,色度为2倍,出水各项指标均达到硫酸工业污染物排放标准(GB 26132—2010)和污水综合排放标准(GB 8978—1996)的要求.再生实验表明,BC-Fe第3次吸附Cd~(2+)和Zn~(2+)的去除率分别为50.6%和49.1%,吸附材料再生性能良好.     

模拟酸雨对水稻叶片质膜H+-ATPase活性与胞内Ca2+浓度的影响

在水培条件下研究了模拟酸雨(pH=2.5～5.5)对水稻叶片胞内Ca2+浓度和质膜H+-ATPase活性的影响.结果表明:与对照组(CK)相比,酸雨处理5 d(胁迫期)后,pH=5.5和5.0处理组的水稻叶片胞内H+浓度、质膜H+-ATPase活性、胞内Ca2+浓度、质膜Ca2+-ATPase活性无显著变化;pH=4.0和3.5处理组各指标显著升高,且H+-ATPase活性随Ca2+浓度升高而上升;pH=3.0和2.5处理组各指标显著降低,此时胞内Ca2+缺失,对H+-ATPase活性的调节作用受到限制.经正常条件培养5 d(恢复期)后,pH=4.0和3.5处理组各指标均恢复至CK的处理水平,表明H+-ATPase活性受到Ca2+调控已恢复到正常;pH=3.0和2.5处理组的Ca2+浓度高于CK及胁迫期,H+-ATPase活性低于CK但高于胁迫期,表明H+-ATPase活性受Ca2+调控得到部分恢复.因此,酸雨胁迫下胞内Ca2+对质膜H+-ATPase活性有一定调节作用,且受酸雨强度的制约.