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(ChloreUa pyrenoidosa)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.     

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.     

Effect of an eco-friendly o/w emulsion stabilized with amphiphilic sodium alginate derivatives on lambda-cyhalothrin adsorption–desorption on natural soil minerals

The effects of amphiphilic O/W emulsions,stabilized by the alkyl polyglycoside(APG)or cholesterol-grafted sodium alginate(CSAD)/APG systems,on lambda-cyhalothrin adsorption/desorption mechanisms on natural soil minerals(i.e.,illite and kaolinite)were investigated.Sorption and desorption of lambda-cyhalothrin onto soil minerals was studied via batch equilibration to give insight into the adsorption equilibrium,kinetics,and thermodynamics of lambda-cyhalothrin adsorption onto minerals.The results indicate the following:(i)The adsorption processes for the APG system and CSAD/APG system include:rapid adsorption,slow adsorption,and adsorption equilibrium.The adsorption kinetics of pesticide on illite and kaolinite are in accordance with the Ho and McKay model,and the adsorption isotherm conforms to the Freundlich model.In addition,the adsorption processes of pesticide for the two systems on minerals were spontaneous and feasible(ΔG~00),endothermic(ΔH~00),and mainly involved chemical bonding(ΔH~060).(ii)The equilibrium adsorption percentages of the pesticide on illite for the APG system and CSAD/APG system were 42.4%and 64.8%,and the corresponding equilibrium adsorption percentages on kaolinite were 40.8%and 61.8%,respectively.Moreover,the pesticide adsorption rate K_(2-CSAD/APG)was faster than K_(2-APG),and its adsorption capacity K_(f-CSAD/APG )was greater than K_(f-APG).Meanwhile,the pesticide desorption K_(fd)in the CSAD/APG system was smaller than that in the APG system.As a result,this eco-friendly O/W emulsion based on amphiphilic sodium alginate derivatives might provide a green pesticide formulation,since it could reduce the amount of lambda-cyhalothrin entering aquatic systems to threaten non-target fish and invertebrate species.     

Investigation of adsorption/desorption behavior of Cr(Ⅵ) at the presence of inorganic and organic substance in membrane capacitive deionization(MCDI)

The adsorption and desorption behavior of Cr(Ⅵ) in membrane capacitive deionization(MCDI) was investigated systematically in the presence of bovine serum albumin(BSA) and KCl with different concentrations, respectively. Results revealed that Cr(Ⅵ) absorption was enhanced and the adsorption amount for Cr(Ⅵ) increased from 155.7 to 190.8 mg/g when KCl concentration increased from 100 to 200 mg/L in the adsorption process, which was attributed to the stronger driving force. However, the adsorption amount sharply decreased to 90.2 mg/g when KCl concentration reached up to 1000 mg/L suggesting the negative effect for Cr(Ⅵ) removal that high KCl concentration had. As for the effect of BSA on ion adsorption, the amount for Cr(Ⅵ) significantly declined to 78.3 mg/g and p H was found to be an important factor contributing to this significant reduction. Then, the desorption performance was also conducted and it was obtained that the presence of KCl had negligible effect on Cr(Ⅵ) desorption, while promoted by the addition of BSA. The incomplete desorption was obtained and the residual chromium ions onto the electrode after desorption was detected via energy-dispersive X-ray spectroscopy(EDS). Based on above analysis, the enhanced removal mechanism for Cr(Ⅵ) in MCDI was found to be consisted of ion adsorption onto electrode surface, the redox reaction of Cr(Ⅵ) into Cr(III)and precipitation, which was demonstrated by X-ray photoelectron spectroscopy(XPS) and scanning electron microscope(SEM).     

Mercury removal using ground and calcined mussel shell

We determined mercury retention on calcined and ground mussel shell, in presence and absence of phosphate, using batch and stirred flow chamber experiments. In batch experiments the calcined shell exhibited higher Hg adsorption, with good fitting to Freundlich equation （R^2： 0.925-0.978）; the presence of phosphate increased Hg adsorption; mercury desorption was 13% or lower, diminishing up to 2% under the presence of phosphates. In stirred flow chamber experiments calcined shell retained more Hg than ground shells （6300 vs. 4000-5200 μmol/kg）; Hg retention increased an additional 40% on calcined shell and up to an additional 70% on ground shells when phosphates were present; mercury desorption was quite similar in all shell types （20%-34%）, increasing up to 49%-60% in ground shells when phosphates were present. The higher Hg adsorption on calcined shell would be related to its calcite and dolomite concentrations; mercury-phosphate interactions would cause the increase in Hg retention when phosphates are present. Data on Hg desorption suggest that Hg retention was not easily reversible after batch experiments, increasing in the stirred flow chamber due to convective flow. Calcined and ground mussel shells could be recycled removing Hg from water, with the presence of phosphates in solution improving efficacy.     

Effects of cadium, zinc and lead on soil enzyme activities

Heavy metal （HM） is a major hazard to the soil-plant system. This study investigated the combined effects of cadium （Cd）, zinc （Zn） and lead （Pb） on activities of four enzymes in soil, including calatase, urease, invertase and alkalin phosphatase. HM content in tops of canola and four enzymes activities in soil were analyzed at two months after the metal additions to the soil. Pb was not significantly inhibitory than the other heavy metals for the four enzyme activities and was shown to have a protective role on calatase activity in the combined presence of Cd, Zn and Pb; whereas Cd significantly inhibited the four enzyme activities, and Zn only inhibited urease and calatase activities. The inhibiting effect of Cd and Zn on urease and calatase activities can be intensified significantly by the additions of Zn and Cd. There was a negative synergistic inhibitory effect of Cd and Zn on the two enzymes in the presence of Cd, Zn and Pb. The urease activity was inhibited more by the HM combinations than by the metals alone and reduced approximately 20%--40% of urease activity. The intertase and alkaline phosphatase activities significantly decreased only with the increase of Cd concentration in the soil. It was shown that urease was much more sensitive to HM than the other enzymes. There was a obvious negative correlation between the ionic impulsion of HM in soil, the ionic impulsion of HM in canola plants tops and urease activity. It is concluded that the soil urease activity may be a sensitive tool for assessing additive toxic combination effect on soil biochemical parameters.     

Particle concentration effect in adsorption/desorption of Zn(Ⅱ) on anatase type nano TiO_2

Adsorption/desorption in a new Zn(Ⅱ)-TiO_2 adsorption system was investigated at different particle concentrations(C_p).TEM,SEM and XRD analyses revealed that the TiO_2 particles were an aggregation of nano-sized(approximately 10 nm)pure anatase-type TiO_2. Adsorption experiments were carried out with particle concentrations of 100,400 and 1000 mg/L,and their adsorption isotherms were found to decline successively,showing an obvious C_p effect.Desorption experiments indicated that adsorption in this system was irreversible,and the irreversibility increased with increasing C_p.These phenomena could be explained by the MEA(metastable equilibrium adsorption)theory and the C_p effect could be modeled well with an MEA-Freundlich-type C_p effect isotherm equation. This study may help understand environmental behavior of contaminants on ultrafine natural particles.     

Investigation of adsorption/desorption behavior of Cr(VI) at the presence of inorganic and organic substance in membrane capacitive deionization (MCDI)

The adsorption and desorption behavior of Cr(VI) in membrane capacitive deionization (MCDI) was investigated systematically in the presence of bovine serum albumin (BSA) and KCl with different concentrations, respectively. Results revealed that Cr(VI) absorption was enhanced and the adsorption amount for Cr(VI) increased from 155.7 to 190.8?mg/g when KCl concentration increased from 100 to 200?mg/L in the adsorption process, which was attributed to the stronger driving force. However, the adsorption amount sharply decreased to 90.2?mg/g when KCl concentration reached up to 1000?mg/L suggesting the negative effect for Cr(VI) removal that high KCl concentration had. As for the effect of BSA on ion adsorption, the amount for Cr (VI) significantly declined to 78.3?mg/g and pH was found to be an important factor contributing to this significant reduction. Then, the desorption performance was also conducted and it was obtained that the presence of KCl had negligible effect on Cr(VI) desorption, while promoted by the addition of BSA. The incomplete desorption was obtained and the residual chromium ions onto the electrode after desorption was detected via energy-dispersive X-ray spectroscopy (EDS). Based on above analysis, the enhanced removal mechanism for Cr(VI) in MCDI was found to be consisted of ion adsorption onto electrode surface, the redox reaction of Cr(VI) into Cr(III) and precipitation, which was demonstrated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM).     

Efficient adsorption of Mn(Ⅱ) by layered double hydroxides intercalated with diethylenetriaminepentaacetic acid and the mechanistic study

In this study, greatly enhanced Mn(II) adsorption was achieved by as-synthesized diethylenetriaminepentaacetate acid intercalated Mg/Al layered double hydroxides(LDHsDTPA). The adsorption capacity of LDHs-DTPA was 83.5 mg/g, which is much higher than that of LDHs-EDTA(44.4 mg/g), LDHs-Oxalate(21.6 mg/g) and LDHs(28.8 mg/g). The adsorption data of aqueous Mn(II) using LDHs-DTPA could be well described by the pseudosecond order kinetics and Langmuir isotherm model. Thermodynamics study results also showed that the adsorption process of Mn(II) by LDHs-DTPA was exothermic as indicated by the negative ΔH value. Furthermore, based on the structural, morphological and thermostable features, as well as FT-IR and XPS characterizations of LDHs-DTPA and the pristine LDHs, the adsorption mechanism of Mn(II) was proposed. The carboxyl groups of DTPA were proposed to be the main binding sites for Mn(II), and the hydroxyl groups of LDHs also played a minor role in the adsorption process. Among the three common regeneration reagents, 0.1 mol/L Na_2CO_3 was the best for reusing LDHs-DTPA in Mn(II)adsorption. Besides, the Mn(II) adsorption performance could be hindered in the presence of typical inorganic ions, especially cations. Further specific modifications of LDHs-DTPA are suggested to get more selective adsorption of Mn(II) in practical applications.     

Mechanism of Cd（II） adsorption by macrofungus Pleurotus platypus

The mechanism of Cd(II) uptake by the dead biomass of macrofungus Pleurotus platypus was investigated using di erent chemical and instrumental techniques. Sequential removal of cell wall components of the biosorbent revealed that structural polysaccharides play a predominant role in the biosorption of Cd(II). The adsorption kinetics fitted well with the pseudo second-order model suggested that the adsorption of Cd(II) on P. platypus involved a chemisorption process. Transmission electron microscopy of the cadmium exposed biomass confirmed the deposition of the metal mainly in the cell wall. Fourier transform infrared spectroscopic analysis of the metal loaded biosorbent confirmed the participation of –OH, –NH and C–O–C groups in the uptake of Cd(II). Energy dispersive X-ray analysis of the biosorbent before and after metal uptake revealed that the main mechanism of adsorption was ion-exchange. The e ectiveness of CaCl2 in the desorption of cadmium perhaps suggested the exchange of Ca2+ with Cd(II).     

聚合氯化铝铁和粘土应急去除蓝藻的室外模拟研究

文章在开展PAFC去除淡水中的铜绿微囊藻影响因素的室内模拟研究基础上进行PAFC和粘土应急去除巢湖水中蓝藻的室外模拟研究。结果表明,在20 mg/L的絮凝剂用量下,聚合氯化铝铁(PAFC)对巢湖水中蓝藻的沉降去除效果优于聚合氯化铝,达到97.7%。PAFC,PAFC和粘土(高岭石或海泡石)可以快速高效絮凝沉降巢湖水中的蓝藻,并且在30 d之内除藻率稳定地维持90.0%以上。同时探讨其对藻毒素释放抑制的影响,结果表明,加入PAFC和粘土(海泡石或高岭石)1 d后能有效地吸附水中的藻毒素,PAFC和海泡石组的吸附去除率大于PAFC和高岭石,且30 d内仍一直维持藻毒素浓度低于对照组。     

不同类型酸修饰-磁化海泡石对水体Cd(II)的吸附研究

采用无机或有机酸修饰-磁化的方法研制海泡石吸附材料H-Sep(盐酸修饰)、N-Sep(硝酸修饰)、P-Sep(磷酸修饰)和A-Sep(醋酸修饰),并借助SEM、TEM、EDS、BET、FT-IR、VSM及XPS等手段表征分析改性前后海泡石的结构特征.同时,在不同投加量、pH、温度和溶液浓度等因素条件下,考察了酸修饰-磁化海泡石对水体Cd(II)吸附效果的影响.结果表明,改性材料取得最佳吸附效果时的投加量为5g·L^-1,pH为6.5,拟合结果更符合准二级动力学方程和Langmuir等温方程.其中,P-Sep的吸附效果最好,其最大理论吸附量为52.6 mg·g^-1.VSM结果表明,H-Sep、N-Sep和A-Sep是磁化分离效果较好的材料,而P-Sep的磁化分离效果不佳.此外,Na⁺、Cl^-等阴阳离子对酸修饰-磁改性海泡石吸附性能没有太大影响,而重金属离子如Pb(II)、Zn(II)会对其吸附过程产生抑制作用.XPS吸附机理分析表明,酸修饰-磁化改性将新的功能基团引入海泡石结构,极大地提升了吸附性能.     

粘土矿物和碳纳米管对微囊藻毒素的吸附

研究了不同粘土矿物和碳纳米管 (CNTs)吸附去除水体中微囊藻毒素 (Microcystins,MCs)的作用 .结果表明 ,在MC RR和LR的初始浓度分别为 2 1 0和 9 5mg·L-1时 ,尽管高岭土和海泡石等粘土矿物对MCs有一定的吸附能力 ,但吸附量分别低于 3 0和 1 6mg·g-1.与测试的不同粘土矿物相比 ,CNTs对MCs的吸附能力较强 ,吸附MC RR和LR量分别达到了 14 8和 6 7mg·g-1,是粘土矿物吸附量的 5倍左右 .进一步研究发现 ,CNTs对MCs的吸附能力随CNTs外径的增加而减少 ,说明CNTs的比表面积是决定吸附MCs量大小的重要因素之一 ,这在如何选择碳纳米管规格用于高效吸附去除水体中MCs方面具有重要意义     

黏土絮凝沉降铜绿微囊藻的动力学及其作用机理

研究了26种天然黏土矿物凝聚沉降铜绿微囊藻的动力学过程在投加量为0.7 g·L^-1时按平衡除藻率和除藻速率将26种黏土分成3类.第1类矿物(滑石、三氧化二铁、海泡石、四氧化三铁、高岭土等)的8 h平衡除藻率大于90%,去除50%藻细胞所需时间t₅₀＜30 min,去除80%藻细胞所需时间t₈₀＜2.5 h第2类黏土(轻质页岩、陶土、凹凸棒、累托土、伊利土等7种)的8 h平衡除藻率为50%～80%,t₅₀＜2.5 h,t80＞5 h.第3类黏土(铁矾土,云母,沸石、浮石、硅藻土、高钾长石和石英等14种)的8 h平衡除藻率低于50%,t₅₀>>8 h.当投加量逐步降低到0.2～0.1 g·L^-1时,25种黏土矿物的8 h平衡除藻率均降到60%以下,只有第1类黏土中的海泡石仍接近90%.与黏土相比,在0.02～0.2 g·L^-1投加量下单独使用聚合氯化铝(PAC)时的8 h平衡除藻率均低于40%.进一步对海泡石进行电性改性后发现,虽然黏土颗粒表面电位的提高(pH 7.4时,Zeta电位由-24.0 mV提高到+0.43 mV)可以显著加快海泡石的除藻速率,但其平衡除藻率并没有显著提高.在分析了本研究中的凝聚机理后提出:架桥网捕作用可能在黏土-藻凝聚过程中发挥了十分关键的作用,增强黏土对藻细胞的架桥网捕作用可能是今后进一步提高除藻效率、大幅度降低投加量的一个重要方向.     

酸热活化、有机化、柱撑改性海泡石对土壤中钒的吸附固定

采用酸热活化、巯基有机化、羟基铁铝柱撑3种方法对天然海泡石进行改性,研究不同改性方法对海泡石结构及比表面积的影响,并将其作为吸附剂加入土壤,采用批量吸附试验考察吸附剂添加量、吸附时间、初始钒V（Ⅴ）离子浓度等因素对吸附效果的影响,探究添加改性海泡石的土壤对V（Ⅴ）的吸附效果及机理。研究结果表明:改性后海泡石比表面积增大,部分结构发生改变,吸附能力增强;添加羟基铁铝柱撑、酸热活化、巯基有机化改性海泡石的土壤对V（Ⅴ）的最大吸附量分别为2159.71,1619.57,936.57 mg/kg;吸附方式为单分子层物理吸附;解吸试验表明,添加羟基有机化改性海泡石的土壤解吸率最高,酸热活化和羟基铁铝柱撑海泡石次之。添加柱撑及酸热活化海泡石的土壤对V的吸附效果较好,用量5%时对V（Ⅴ）的固化率分别为30.24%、22.67%,但柱撑海泡石的稳定性仍有待提升。     

Adsorption of zinc on manganite(γ-MnOOH): particle concentration effect and adsorption reversibility

The adsorption and desorption processes of Zn(Ⅱ) on τ-MnOOH as a function of particle concentrations (Cp) were studied. An obvious Cp effect was observed in this adsorption system. The degree of adsorption hysteresis increased greatly with the increasing of Cp, indicating that the extent of the real metastable-equilibrium states deviating from the ideal equilibrium state was enhanced with the increasing of Cp. The Cp-reversibility relationship confirmed the metastable-equilibrium adsorption (MEA) inequality (Pan, 1998a), which was the core formulation of the MEA theory. Because the MEA inequality was based on the basic hypothesis of MEA theory that adsorption densitιy ι is not a state variable, the Cp-reversibility relationship gave indirect evidence to the basic hypothesis of MEA theory.     

Synthesis, characterization, and adsorption performance of Pb（Ⅱ）-imprinted polymer in nano-TiO2 matrix

Surface ion-imprinted in combination with sol-gel process was applied to synthesis a new Pb(II)-imprinted polymer for selective separation and enrichment of trace Pb(II) from aqueous solution. The prepared material was characterized by using the infrared spectra, X-ray di ractometer, and scanning electron microscopy. The batch experiments were conducted to study the optimal adsorption condition of adsorption trace Pb(II) from aqueous solutions on Pb(II)-imprinted polymer. The equilibrium was achieved in approximately 4.0 h, and the experimental kinetic data were fitted the pseudo second-order model better. The maximum adsorption capacity was 22.7 mg/g, and the Langmuir equation fitted the adsorption isotherm data. The results of selectivity experiment showed that selectively adsorbed rate of Pb(II) on Pb(II)-imprinted polymer was higher than all other studied ions. Desorption conditions of the adsorbed Pb(II) from the Pb(II)-imprinted polymer were also studied in batch experiments. The prepared Pb(II)-imprinted polymer was shown to be promising for the separation and enrichment of trace Pb(II) from water samples. The adsorption and desorption mechanisms were proposed.     

铊在河流沉积物上的吸附解吸行为研究

水体环境条件的改变直接影响铊在水体沉积物的吸附解吸行为,进而影响到铊在水环境中的迁移、转化途径.本实验采用北京市凉水河(L8)及其沿岸的藕田(L6)沉积物作为研究对象,研究了Tl(Ⅰ)在沉积物上的吸附特征及pH对其吸附过程的影响,并考察了以沉积物浸出液和背景电解质作为解吸体系时,Tl(Ⅰ)自沉积物上解吸的变化情况.研究结果表明:①两种沉积物对铊的吸附速度较快,初始的5 min内,沉积物对铊的吸附量达到最大吸附量的90％ (L6)和80％(L8)以上,12h基本达到吸附平衡.②沉积物L6和L8对Tl(I)吸附量均随着初始浓度的升高而增大,但是L6的吸附量明显高于L8.两种沉积物对铊的吸附等温线用Freundlich方程和Langmuir方程拟合均得到较好的拟合结果,在分析吸附解吸机理时,Langmuir方程更能说明其物理化学意义.③pH对铊在沉积物上的吸附影响较大,随着体系pH的增大,吸附量逐渐增大.④沉积物浸出液的高效体积排阻色谱和三维荧光表征结果表明沉积物浸出液中主要以类蛋白和腐殖酸类物质为主,荧光强度集中在1100 ～1550之间.用沉积物浸出液代替背景电解质作为解吸体系时,解吸量增加了2.232 mg·kg-1(L6)和1.494 mg·kg-1(L8)(C0 =0.33 mg·L-1),铊更易从沉积物浸出液的环境下解吸下来,进入水体.     

有机改性粘土去除赤潮生物的机制研究

研究了季铵化合物改性粘土的制备条件对其去除赤潮藻效果的影响,探讨了该粘土体系高效除藻的机制.实验表明,十六烷基三甲基铵(HDTMA)可以有效地提高粘土的絮凝能力,同时HDTMA改性粘土中含有亚稳态HDTMA,增加了该改性粘土对赤潮生物的灭杀能力.改性粘土去除赤潮藻的能力与所吸附季铵化合物的杀藻能力、吸附量正相关,当老化时间延长、吸附季铵化合物稳定性增强时改性粘土除藻能力大大降低.结构不同的粘土对于吸附HDTMA的稳定化产生的空间阻力不同,在吸附量相同的情况下3层结构的蒙脱土中会有更多的亚稳态HDTMA产生;由于同离子效应,反应介质中高价金属阳离子的存在提高了亚稳态HDTMA的量,因此相应的改性粘土具有更高的赤潮藻去除能力.在60℃条件下吸附的HDTMA会更有效地占据粘土中的阳离子交换位,达到稳定态;而升高或降低温度都会有利于亚稳态HDTMA的出现,相应的改性粘土具有更高的赤潮藻去除能力.