Study on polyepoxysuccinic acid reverse osmosis scale inhibitor

The effectiveness and applicability of polyepoxysuccinic acid (PESA) as a reverse osmosis (RO) scale inhibitor were studied using static and dynamic methods. In the static study, PESA performed very well in the treatment of water samples with various types of scale that commonly exist in RO water (i.e., CaCO₃, CaSO₄, BaSO₄, SrSO₄), showing an average scale inhibition ratio of above 90% at a dosage of 10 mg/L. SEM analysis showed a disordered CaCO₃ crystal in the presence of PESA, suggesting the scale-inhibiting mechanism. In the dynamic experiment, PESA also showed great performance in the treatment of 10 samples of synthetic tap water or sea water with different ion composition (i.e., Ca²⁺, HCO₃^?, Fe³⁺, Al³⁺). After one cycle (7 d) of RO treatment of each sample at full recycle operation mode under a constant pressure of 1×10⁶ Pa, the differences in water permeability and desalination ratio among samples are within 5%, suggesting that PESA is capable of treating waters of different quality, and has a strong resistance to ions that are harmful to scale inhibiting (i.e., Fe³⁺ and Al³⁺). All these results suggest that PESA should be an effective scale inhibitor that is applicable to RO treatment of waters with a wide range of ion compositions.     

混凝沉淀和机械过滤组合工艺处理含磷废水

利用二级混凝沉淀+机械过滤器法处理含磷废水,通过做pH、CaCl2的投加量对除磷处理效果影响的小试,确定混凝沉淀最佳条件为pH值为11和CaCl2投加量100mg/L.工程运行现状表明:该法处理磷化废水是可行的,出水能够达到国家污水综合排放标准(GB8978-1996)一级排放标准.     

Determination of the dissociation constants of polyepoxysuccinic acid

The dissociation constants of polyepoxysuccinic acid (PESA) were investigated in this study. Based on the potentiometric titration and the BEST program, the dissociation constants of PESA were determined. Considering the complexity of the dissociation of PESA in aqueous solution, several models were constructed to simulate the dissociation process of PESA. By comparison, the dissociation constants of PESA were obtained with model 4. The species distribution of PESA in aqueous solution as a function of pH was also presented according to the experimental and calculation results. It showed that the H₂L model with five basic structure units to describe the dissociation of PESA was reasonable, and the relevant constants had less error and better matching between the experimental and calculation data. The corresponding values of pK _ai were 4.68 and 4.92, respectively, for H₂L at 35°C with ionic strength of 0.1 mol/L.     

电-Fenton法降解低含盐量反渗透浓缩液中腐植酸

为研究采用碳毡-Pt电-Fenton体系处理模拟低含盐量反渗透浓缩液中的腐植酸的影响因素和降解机制,通过单因素试验,以COD_Cr去除率为评价指标,以Fe2+添加量、通氧量、电流密度、pH为考察因素,探讨了不同条件对电-Fenton体系ρ（H₂O₂）和COD_Cr去除率的影响.结果表明:采用电-Fenton法降解模拟反渗透浓缩液,较低的含盐量有助于COD_Cr的去除,与高含盐量（1 000~2 000 mg/L）相比,在低含盐量（500~1 000 mg/L）条件下COD_Cr去除率提高10%~20%;并且最佳条件下实际电流效率（GCE）达到15.6%,电化学能耗为32 kW·h/kg.最佳反应条件:通氧量为0.3 m3/L,Fe2+添加量为0.1 mmol/L,电流密度为3.5 mA/cm2,pH=3,在该条件下反应180 min时,电-Fenton体系产生的ρ（H₂O₂）为105 mg/L,可使ρ（COD_Cr）由150 mg/L降至16 mg/L,COD_Cr去除率达到90%.研究显示,较宽的pH范围（3~7）内碳毡-Pt电-Fenton体系对腐植酸的降解表现稳定,COD_Cr去除率均达到60%以上.      

纳米四氧化三铁对2,4-D的脱氯降解

采用纳米四氧化三铁(Fe3O4)降解水溶液中的2,4-二氯苯氧乙酸(2,4-D),考察了2,4-D初始浓度、纳米Fe3O4投加量、溶液pH和温度等因素对2,4-D降解率的影响.结果表明,纳米Fe3O4对2,4-D有显著的降解效果,初始浓度为10 mg/L的2,4-D, 48 h内降解率可达48%.纳米Fe3O4对2,4-D的降解是一个还原脱氯过程,反应体系中氯离子浓度随2,4-D浓度降低而升高.LC/MS分析表明,2,4-D降解的主要产物是苯酚,其他中间产物是2,4-二氯苯酚(2,4-DCP)、4-氯苯酚(4-CP)和2-氯苯酚(2-CP).溶液中2,4-D的降解符合准一级反应动力学,产物4-CP、2,4-DCP和苯酚的反应速率常数K分别为0.0043、0.0026和0.0032 h -1.环境条件对降解效率有显著影响,2,4-D初始浓度在0～10 mg/L、纳米Fe3O4投加量0～300 mg/L的范围内,2,4-D降解率随初始浓度和纳米Fe3O4投加量的增加而增大;pH对2,4-D的脱氯降解有显著影响,在pH为3.0时,纳米Fe3O4对2,4-D的还原脱氯效果最好;温度升高,可以提高脱氯反应速率.     

铁盐和铝盐混凝对水中天然有机物的去除特性研究

以三氯化铁和硫酸铝为研究对象,探讨了2种混凝剂对水中天然有机物的去除效果及特点.结果表明,低投量下,硫酸铝对天然有机物的去除效果要好于三氯化铁,混凝剂投量高于15mg/L时,三氯化铁的效果较好.如混凝剂投量为10mg/L时,硫酸铝和三氯化铁处理水的TOC分别为4.19mg/L和9mg/L;当混凝剂投量为20mg/L时, TOC分别降至2.44mg/L和1.69mg/L.三氯化铁混凝后水的pH值降低幅度高于硫酸铝,形成的水解产物所带正电荷密度升高,水中有机物的质子化程度高,有利于对有机物的吸附去除.通过对UV254出和SUVA的考察可知,三氯化铁对共轭结构及不饱和有机物的去除能力要高于硫酸铝.2种混凝剂对水中不同性质有机物的去除效果不同,三氯化铁对亲水性有机物去除效果较好,对小分子量有机物去除高于硫酸铝,如混凝剂投量为20mg/L时,三氯化铁和硫酸铝对相对分子质量区间小于10 000的有机物去除率分别为16.4%和6.1%,而硫酸铝对大分子量有机物去除效率较高.     

O3/H2O2降解Atrazine效能研究

利用O₃/H²O²降解莠去津,对氧化产物进行了色谱分析,以评价该体系降解莠去津效能.莠去津初始浓度2 mg/L,7.5 mg/L的O₃单独氧化去除率为27.2%;相同O₃投量下,H²O²/O₃摩尔比0.75时,5 min莠去津的去除率最高可达96.5%,表明H²O²/O₃体系对莠去津的去除效果良好,降解速度快.以离子色谱对产物的离子进行分析,莠去津浓度下降的同时,硝酸根和氯离子浓度增高.GC-MS检测的产物和对LC-MS谱图的分析表明,有机产物中存在脱乙基、脱异丙基和脱氯莠去津,说明H²O²/O₃并不能彻底氧化莠去津,因此工程中作为主要去除单元或突发性污染事件的应急手段可能还需要与活性炭等单元联用.     

Response of soil catalase activity to chromium contamination

The impact of chromium(III) and (VI) forms on soil catalase activity was presented. The Orthic Podzol, Haplic Phaeozem and Mollic Gleysol from di erent depths were used in the experiment. The soil samples were amended with solution of Cr(III) using CrCl3, and with Cr(VI) using K2Cr2O7 in the concentration range from 0 to 20 mg/kg, whereas the samples without the addition of chromium served as control. Catalase activity was assayed by one of the commonly used spectrophotometric methods. As it was demonstrated in the experiment, both Cr(III) and Cr(VI) have an ability to reduce soil catalase activity. A chromium dosage of 20 mg/kg caused the inhibition of catalase activity and the corresponding contamination levels ranged from 75% to 92% for Cr(III) and 68% to 76% for Cr(VI), with relation to the control. Catalase activity reached maximum in the soil material from surface layers (0–25 cm), typically characterized by the highest content of organic matter creating favorable conditions for microorganisms.     

不同铁氧化物对小麦幼苗镉积累的影响

小麦富镉（Cd）问题受到广泛关注,铁氧化物具备降镉潜力.通过盆栽小麦幼苗实验,分析了三氧化二铁（Fe₂O₃）、氢氧化铁[Fe（OH）₃]及拜耳法赤泥（B-RM）3种铁氧化物的降镉能力.结果显示3种铁氧化物中,Fe（OH）₃可显著降低小麦幼苗茎叶Cd含量,与对照相比降幅为16.3%~27.7%,投加量为0.5%时降Cd效果最优.Fe（OH）₃能够显著降低小麦幼苗根部向茎叶的Cd转运,投加量为10%时富集系数及转运系数最低.小麦幼苗根际土壤Fe/Cd、Cu/Cd及Zn/Cd是影响小麦幼苗茎叶Cd积累的关键因子,当Fe/Cd>25000、Cu/Cd > 50或Zn/Cd > 100时,根际土壤元素比与茎叶镉含量呈显著负相关.该比值的确定对于大田应用中钝化剂材料投加量的确定具有指导意义.     

UV/H2O2/草酸铁处理垃圾渗滤液的研究

利用UV(125 W)/H₂O₂/草酸铁处理已经过生化处理的垃圾渗滤液(CODCr为450 mg/L)时,反应较佳条件是pH值为4.0及总药剂用量为14 mL/L.草酸铁的用量要适当,投加量过少,混凝效果较差,有效光子不能完全转化为化学能,处理效果不理想;投加量过多,溶液形成棕色混浊,使紫外光的吸收降低,造成光散射,降低反应速度.而H₂O₂的投加量过多,将使铁的络合物更加稳定,H₂O₂的分解速率受到限制,投加量过少,效果也会降低.当总药剂用量为14 mL/L(其中30%过氧化氢6 mL/L,0.1 mol/L草酸铁溶液8 mL/L)时,反应30 min后,CODCr去除率可达80%左右,脱色率可达90%以上.      

Simultaneous removal of Cu(II) and Cr(VI) by Mg–Al–Cl layered double hydroxide and mechanism insight

Mg–Al–Cl layered double hydroxide (Cl-LDH) was prepared to simultaneously remove Cu(II) and Cr(VI) from aqueous solution. The coexisting Cu(II) (20 mg/L) and Cr(VI) (40 mg/L) were completely removed within 30 min by Cl-LDH in a dosage of 2.0 g/L; the removal rate of Cu(II) was accelerated in the presence of Cr(VI). Moreover, compared with the adsorption of single Cu(II) or Cr(VI), the adsorption capacities of Cl-LDH for Cu(II) and Cr(VI) can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu(II) (200 mg/L) and Cr(VI) (400 mg/L). The affecting factors (such as solution initial pH, adsorbent dosage, and contact time) have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg²⁺ and Al³⁺ in relevant solutions were monitored. To get the underlying mechanism, the Cl-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr(VI) with Cl⁻ in Cl-LDH interlayer, isomorphic substitution of Mg²⁺ with Cu²⁺, formation of Cu₂Cl(OH)₃ precipitation, and the adsorption of Cr(VI) by Cu₂Cl(OH)₃. This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by Cl-LDH.     

Comparative cytotoxicity of nanoparticles and ions to Escherichia coli in binary mixtures

The objective of this study was to understand toxicity of mixture of nanoparticles (NPs) (ZnO and TiO₂) and their ions to Escherichia coli. Results indicated the decrease in percentage growth of E. coli with the increase in concentration of NPs both in single and mixture setups. Even a small concentration of 1 mg/L was observed to be significantly toxic to E. coli in binary mixture setup (exposure concentration: 1 mg/L ZnO and 1 mg/L TiO₂; 21.15% decrease in plate count concentration with respect to control). Exposure of E. coli to mixture of NPs at 1000 mg/L (i.e., 1000 mg/L ZnO and 1000 mg/L TiO₂) resulted in 99.63% decrease in plate count concentration with respect to control. Toxic effects of ions to E. coli were found to be lesser than their corresponding NPs. The percentage growth reduction was found to be 36% for binary mixture of zinc and titanium ions at the highest concentration (i.e., 803.0 mg/L Zn and 593.3 mg/L Ti where ion concentrations are equal to the Zn ions present in 1000 mg/L ZnO NP solution and Ti^+ 4 ions present in 1000 mg/L TiO₂ NP solution). Nature of mixture toxicity of the two NPs to E. coli was found to be antagonistic. The alkaline phosphatase (Alp) assay indicated that the maximum damage was observed when E. coli was exposed to 1000 mg/L of mixture of NPs. This study tries to fill the knowledge gap on information of toxicity of mixture of NPs to bacteria which has not been reported earlier.     

Effects of metal ions on the catalytic degradation of dicofol by cellulase

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, K_m, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, V_max, was 0.40 mg/L/min, while that of free cellulase was K_m = 8.18 mg/L, and V_max = 0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn^2 +, reversible competition with Cd^2 +, and irreversible inhibition by Pb^2 +. Ca^2 + promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment.     

水中安乃近高级氧化法去除及其产物的毒性评价

在实验室规模下,利用UV、H2O2、UV/H2O2、Fenton和UV/Fenton等高级氧化技术降解安乃近并对其降解产物进行毒性评价.在对各参数(pH值、H2O2投加量、Fe2+投加量、光照时间)优化的基础上,用TOC去除率和降解率对降解效果进行评价.安乃近及其光催化降解中间产物在水溶液中的毒性通过其对普通小球藻的生长抑制作用评价,并以96h的半数效应浓度(EC50)表示.结果表明,UV/Fenton对安乃近的降解率最大(96%),最佳降解条件为pH3,Fe2+、H2O2浓度分别为2,140mg/L.初期降解产物的生物毒性比母体化合物大,其EC50达到最小值(13.65mg/L),随降解时间的延长,EC50值逐渐增大,在180min为44.07mg/L,小球藻生长状况良好,表明含低浓度安乃近的水溶液经过UV/Fenton法处理后对水中生物已不具有危害作用.     

Research on orthogonal coagulated setting and coagulation-flotation test of tannery wastewater

The treatment of the tannery wastewater was studied by orthogonal test of beaker coagulation. FeSO₄ and alkaline sodium aluminum waste liquid contained NaOH-NaAlO₂ were used as flocculants, with polyacrylamide (PAM) as coagulation. When the dosage of FeSO₄ was 2.66 g/L (pH 5.5), the wastewater pH value of adding alkaline sodium aluminum waste liquid was 8, and the dosage of PAM was 1 mg/L, the optimum result was obtained. A test device of co-coagulation flotation reactor was designed on the basis of the conglutination of bubble, flocci and turbulent flotation theory. In the device, the gas-1iuid mixed pump substituted the air compressor and the pressure releaser. The combination of coagulation and air flotation were realized. The pump is a new kind of air saturation equipment. The air compressor and the pressure releaser were used commonly in traditional air flotation device. The results of treatment of the tannery wastewater showed a stable state, when the operating pressure was 5×10⁵ Pa, circumfluence ratio was 225%.     

强化混凝对腐殖酸和富里酸去除对比研究

以腐殖酸和富里酸为研究对象,考察了硫酸铝、三氯化铁、聚合氯化铝和聚合氯化铁这4种混凝剂的强化混凝效果,并研究了pH、浊度及Ca2+、腐殖酸和富里酸相对含量对强化混凝的影响.结果表明,4种混凝剂对腐殖酸的去除效果要高于富里酸,三氯化铁和硫酸铝比聚合氯化铝和聚合氯化铁具有更好的混凝效果,在混凝剂投量为40 mg.L-1时,三氯化铁、硫酸铝、聚合氯化铁和聚合氯化铝混凝后可将水样中富里酸浓度由10 mg.L-1分别降为3.22、4.34、5.85和4.86 mg.L-1,而腐殖酸浓度可分别降至1.13、2.13、3.44和2.50 mg.L-1.三氯化铁和硫酸铝强化混凝的最佳pH为5.5～6.5,在其它pH范围强化混凝效果降低;水样中有机物浓度越高,混凝效果越差,富里酸/腐殖酸>0.4后混凝效果明显变差.浊度对混凝剂去除有机物的影响较小,Ca2+浓度的增加可提高腐殖酸和富里酸的去除效果.     

甲苯硝化废水的微电解-Fenton氧化预处理

采用铁碳微电解-Fenton氧化联合工艺处理甲苯硝化废水,探讨了溶液pH值、铁炭投加量、铁炭比例、H2O2投加量和反应时间等因素对微电解-Fenton氧化处理硝化废水的影响规律,获得微电解-Fenton氧化处理硝化废水的最佳工艺条件:废水pH在3左右,铁炭投加量为0.6 g/L,Fe/C质量比为4∶1,反应时间为1.5h,微电解后H2O2投加量为20 ml/L,反应时间为1 h。硝化废水经微电解-Fenton氧化处理后,COD由29 146mg/L降至6 477 mg/L,COD去除率达77.8%,BOD5/COD由0提高到0.37左右,废水可生化性显著增强。     

铝盐混凝剂的混凝效果与残留铝含量和组分之间的关系研究

研究了氯化铝、硫酸铝、聚合氯化铝(poly-aluminum chloride, PAC)3种铝盐混凝剂在腐殖酸-高岭土模拟水样中的应用,以比较3种混凝剂在该水样中的混凝效果与残留铝含量和组分之间的关系.结果表明, 3种铝盐混凝剂在试验选取的投加量下对浊度和UV254的去除率最高可达90%左右,PAC能在较高的投加量下达到较好的混凝效果;较高投加量下PAC混凝沉淀出水中残留总铝含量为0.9 mg/L左右,余铝率为-3.0%左右,均明显低于传统的铝盐混凝剂;3种混凝剂混凝处理腐殖酸-高岭土模拟水样时,残留铝均大部分以溶解性总铝的形式存在,且溶解性有机铝在总溶解性铝中所占比例较大;PAC在腐殖酸-高岭土混凝沉淀出水中残留总铝的含量下降最快,且能够有效降低出水中毒性较大的溶解性铝的含量,其混凝沉淀出水中残留总溶解性铝含量为0.6 mg/L左右.     

Hydroxyl carboxylate based non-phosphorus corrosion inhibition process for reclaimed water pipeline and downstream recirculating cooling water system

A combined process was developed to inhibit the corrosion both in the pipeline of reclaimed water supplies (PRWS) and in downstream recirculating cooling water systems (RCWS) using the reclaimed water as makeup. Hydroxyl carboxylate-based corrosion inhibitors (e.g., gluconate, citrate, tartrate) and zinc sulfate heptahydrate, which provided Zn^2 + as a synergistic corrosion inhibition additive, were added prior to the PRWS when the phosphate (which could be utilized as a corrosion inhibitor) content in the reclaimed water was below 1.7 mg/L, and no additional corrosion inhibitors were required for the downstream RCWS. Satisfactory corrosion inhibition was achieved even if the RCWS was operated under the condition of high numbers of concentration cycles. The corrosion inhibition requirement was also met by the appropriate combination of PO₄^3 − and Zn^2 + when the phosphate content in the reclaimed water was more than 1.7 mg/L. The process integrated not only water reclamation and reuse, and the operation of a highly concentrated RCWS, but also the comprehensive utilization of phosphate in reclaimed water and the application of non-phosphorus corrosion inhibitors. The proposed process reduced the operating cost of the PRWS and the RCWS, and lowered the environmental hazard caused by the excessive discharge of phosphate. Furthermore, larger amounts of water resources could be conserved as a result.     

不同形态锌离子对鲫鱼谷胱甘肽系统的影响

研究了在室内模拟条件下,不同形态锌离子(Zn²⁺与Zn-EDTA)长期(40d)暴露对鲫鱼(Crucian curatus)肝脏谷胱甘肽系统的影响.结果表明,在试验剂量范围内,0.10mg/L的Zn²⁺暴露即能引起鲫鱼肝脏中锌显著积累,明显高于Zn-EDTA暴露试验中的积累量.鲫鱼肝脏中谷胱甘肽还原酶(GR)的活性,在Zn²⁺及Zn-EDTA浓度为0.05mg/L(低于渔业水质标准0.10mg/L)时就受到了显著抑制,Zn-EDTA较高浓度(>0.1mg/L)暴露对GR活性的抑制率更大.Zn²⁺对谷胱甘肽过氧化物酶(GPx)活性、氧化型谷胱甘肽(GSSG)、还原型谷胱甘肽(GSH)的含量及GSH/GSSG均有抑制作用,且存在良好的剂量-效应关系.