生物炭/铁酸锰对Zn^2+和Cu^2+的吸附性能试验

为探求吸附效果好、回收方便的吸附剂以解决重金属污染废水的处理难题,以玉米秸秆和铁酸锰为原料,通过溶胶-凝胶法以蛋清为络合剂经热解制备了一种生物炭/铁酸锰(BC/FM)复合材料,在对该复合材料扫描电子显微镜(SEM)和磁滞回线分析的基础上,进行了去除废水中Zn^2+、Cu^2+的吸附试验。结果表明,铁酸锰可有效地负载到生物炭上,形成官能团丰富、磁性良好的复合材料;BC/FM对Zn^2+、Cu^2+的吸附最佳pH值分别为5和6,并均在90 min达到吸附平衡,准二级模型能更好地描述BC/FM对Zn^2+、Cu^2+吸附过程;Langmuir模型拟合曲线和Freundlich模型拟合曲线分别适用于描述BC/FM对Zn^2+、Cu^2+的等温吸附过程,且均为自发吸热反应;BC/FM对Zn^2+、Cu^2+吸附机制主要为络合反应。     

天然硅藻土吸附废水中Cd2+和Pb2+的热力学研究

用天然硅藻土吸附废水中Cd2和Pb2+两种重金属离子,探讨了天然硅藻土对Cd2+和pb2+的吸附等温式和吸附热力学规律.结果表明:天然硅藻土对Cd2+和pb2+的平衡吸附量随温度的升高而增加.两种重金属离子的吸附等温式都与Langmuir方程符合更好.由热力学参数可知吸附过程是自发、吸热的过程.     

不同pH调控方法对电助淋洗去除农田土壤Cd的影响

淋洗是修复土壤的一种简单高效的方法,但是对于渗透性系数低的土壤效果不佳。因此,采用电动修复技术强化农田重金属Cd的淋洗(简称电助淋洗),探讨了不同电解液pH控制方法对电助淋洗去除重金属Cd的影响。研究结果表明在电压梯度为1.5 V/cm、间歇通电5 d,每天连续通电8 h条件下,电助淋洗试验Ex1中重金属Cd的去除率为50.87%,比单一淋洗试验组Ex0中重金属Cd的去除率高10%;电动修复技术能强化土壤中孔隙水的流动,加速重金属离子的迁出,提高重金属去除率,有效促进农田土壤重金属Cd的淋洗效果。对比不控制电解液pH的试验Ex1和控制电解液pH的试验Ex2,Ex3,Ex4可知,控制电解液pH能控制土壤pH值,提高重金属Cd的迁移率。综合考虑现场操作等因素,建议采用电极极性切换控制土壤pH值。     

城市地表径流胶体对重金属下渗迁移行为的影响

为了解城市地表径流胶体对重金属在下渗设施中迁移行为的影响,提取道路雨水径流中的胶体,采用下渗柱试验研究了存在径流胶体时Cu~(2+)、Pb~(2+)和Cd~(2+)的下渗迁移出流质量浓度变化,分析进水流速、pH值、Na~+浓度、重金属离子共存和胶体粒径对胶体携带重金属迁移行为的影响。结果表明:径流胶体能够促进重金属离子的下渗迁移;进水流速越高,径流胶体对重金属离子的携带迁移作用越明显;弱酸性条件更有利于径流胶体对重金属离子的携带迁移;雨水径流中存在Na~+或多种重金属离子共存时,胶体携带重金属离子的下渗迁移过程会受到抑制,且离子浓度越大,其受抑制作用越明显;胶体粒径会显著影响径流胶体对重金属离子的携带迁移能力,胶体粒径越小,越容易携带重金属离子下渗迁移。     

Application of mulch for treating metals in urban runoff: batch and column test.

Among the many methods available for the removal of heavy metals in urban nonpoint source pollution (NSP), adsorption has been shown to be an economically feasible alternative. To adsorb the amount of heavy metals in runoff, filtration of runoff through a specially constructed filter system is one possible treatment method. The mulch layer in a specially constructed filter system functions through adsorptive-filtration, where some pollutants are immobilised through sorption and some pollutants associated with suspended solids are immobilised through filtration. Therefore, the major interest of this study was to investigate the possibility of utilising mulch for the adsorption of heavy metals such as cadmium, copper, lead and zinc for a solution typical of those found in urban runoff using the flask-type adsorption batch tests and laboratory column tests. From the equilibrium sorption batch tests, it was observed that the adsorption of heavy metals on mulch with the same initial concentrations of metals in the solution decreased in the order Pb(II) > Cu(II) > Zn(II) > Cd(II) regardless of changes in pH. In column tests, the breakthrough curves for various heavy metals' adsorption by mulch showed that the binding strength of the following metal ions onto mulch was as follows: Pb(II) > Cu(II) > Zn(II) > Cd(II).     

泥沙粒径对铜离子吸附贡献率的影响研究

含有重金属的工业废水排放到河道中,通过河道底泥的吸附作用,不断累积到底泥中,对环境和人类健康构成威胁。研究河涌底泥重金属吸附特性,对于解决重金属污染问题具有科学意义和现实价值。该文通过研究泥沙粒径对底泥吸附铜离子的影响规律,分析泥沙粒径对于铜离子的吸附量和吸附速率的影响特征。结果表明:在相同条件下,随着泥沙粒径的增大,泥沙对铜离子吸附速率的贡献率随之增大,粗颗粒泥沙的吸附速度要比细颗粒泥沙的迅速的多;而随着粒径的增大,泥沙对铜离子吸附量的贡献率随之减小,细颗粒泥沙的吸附量则远大于粗颗粒泥沙。     

咸水在黏性土中迁移转化的试验研究

采用衡水地下水科学试验场浅层钻孔土样进行室内一维土柱渗流试验,并用地球化学模拟方法探讨黏性土对咸水迁移转化的控制机理。结果表明:黏性土对咸水迁移有一定的阻隔作用,1号土柱对Na+的阻滞作用以吸附为主,2号土柱对Na+的阻滞作用由吸附和阳离子交换共同影响;1号和2号土柱的阻盐率分别为49.8%和54.5%;1号和2号土柱中黏性土的阻滞因子R1和R2分别为1.54和3.78;咸水迁移过程中,控制水岩相互作用的主要因素是岩盐的沉淀,石膏、方解石的溶解,Mg2+、Ca2+与Na+之间的离子交换。     

Removal of toxic heavy metals by iron-coated starfish.

In this study, the applicability of calcined starfish (SF) and iron-coated SF (ICSF) as potential adsorbents for the treatment of wastewater containing heavy metal ions was evaluated. ICSF was prepared by mixing FeCl(3) solution previously adjusted to pH 7 approximately 9 with SF at 105 degrees C. From the dissolution test at pH 2, ICSF showed strong acid-proof properties. In the batch adsorption, Cu(II) adsorption onto ICSF was completed within 150 minutes, while 47% Cu(II) was removed with SF alone. This result clearly suggests that the coated Fe(III) serves additional adsorption sites, resulting in the enhanced removal of heavy metal ions. The removed fraction of both Cu(II) and Pb(II) increased with increasing solution pH and nearly complete removals of Pb(II) and Cu(II) were observed at around pH 6 and 8, respectively. From the adsorption isotherm of Cu(II) onto SF and ICSF at pH 3.0, the removed amount of Cu(II) by ICSF was greater than that by SF over the entire concentration range studied. In the column test, the breakthrough of Cu(II) in the ICSF column was greatly retarded compared to that in the SF column. Based on the drinking water regulations for Cu(II), SF and ICSF were able to remove 3400 and 8600 mg/kg of Cu(II) from the wastewater, respectively.     

利用土柱试验快速测试重金属对流-弥散-吸附参数的方法

重金属离子对流-弥散-吸附参数对于评价防污屏障的服役性能十分重要,目前还缺乏高效且可靠的方法系统地测试这些参数。为了能在较短试验时间内采用较少试验数量获得重金属离子对流-弥散-吸附参数,以Pb²⁺作为代表性重金属离子,开展了Pb²⁺在土-膨润土中的土柱试验。结果表明:模型渗流流速从0增大到1.59×10^-7 m/s时, Pb²⁺的阻滞因子R_d从13减小为11,符合流速越大阻滞因子越小的规律;该土柱试验方法得到的Pb²⁺对流-弥散-吸附参数与文献报道的参数典型取值高度一致,证明了该方法的有效性;该方法减少了试验数量,提高了参数获取效率,且以单参数解耦方式拟合试验结果,拟合结果更可靠。研究结果为防污屏障材料的服役性能评价提供新的途径。     

Heavy metal adsorption changes of EAF steel slag after phosphorus adsorption

A kind of electric arc furnace (EAF) steel slag was phosphated, and its isothermal and dynamic adsorptions of copper, cadmium, and lead ions were measured to determine if heavy metal adsorption changes after phosphorus adsorption. The surface area increased greatly after the slag was phosphated. Isothermal adsorption experiments showed that the theoretical Q(max) of the EAF steel slag on Cu(2+), Cd(2+), and Pb(2+) improved 59, 50, and 89% respectively after it was phosphated. Dynamic adsorption results showed that the greatest adsorption capacities of unit volume of Cu(2+), Cd(2+), and Pb(2+) were 2.2, 1.8, and 1.8 times that of the column packed with original EAF steel slag when the column was packed with phosphate EAF steel slag at the same heavy metal ion concentration. The breakthrough time, the exhaustion time and elution efficiency of the column also increased when the column was packed with phosphated EAF steel slag compared with that packed with original EAF steel slag. Phosphorus adsorption could further improve the heavy metal ion adsorption of the EAF steel slag.     

Use of citric acid for heavy metals extraction from contaminated sewage sludge for land application.

Recent studies revealed that organic acids such as citric and oxalic acids seemed to be more promising as chemical extracting agents for removal of heavy metals from contaminated sludge, since they are biodegradable and can attain a higher metal extraction efficiency at mildly acidic pH compared to other extracting agents. Results of a lab-scale study on the efficiency of citric acid in the extraction of chromium (Cr), copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) from anaerobically digested sludge, revealed that citric acid seemed to be highly effective in extracting Cr (at 100%), Cu (at 88%), Ni (at 98%) and Zn (at 100%) at pH 2.33, mostly at 5 days leaching time except for Cu and Zn, which are at 1 day and 2 h contact times respectively. Lead removal at the same pH was also high at 95% but at a longer leaching time of 11 days. At pH 3, citric acid seemed to be highly effective in extracting Pb (at 100%) at 1 day leaching time, although higher removals were also attained for Ni (70%) and Zn (80%) at only 2 h leaching time. Chemical speciation studies showed that Cr, Cu and Ni in the sludge sample seem to predominate in residual fractions, while Pb and Zn were found mostly bound to organic and inorganic matter forms, hence the potential of the sludge for land application.     

催化铁/混凝法预处理酸性化工废水pH变化规律及混凝最佳工况研究

pH值是催化铁法预处理酸性化工废水主要考察指标,是Fe2+产生量和混凝效果的控制因素,为此进行了催化铁预处理化工废水pH值变化和Fe2+产生规律及后继混凝效果的研究。结果表明:催化铁反应最适初始pH为2.75,反应时间为1 h;混凝反应最佳条件为:Fe2+浓度为120 mg/L,pH控制在8.0～8.5;系统COD去除率为56.8%,色度去除率为92%;催化铁处理后的化工废水与印染废水混合进行混凝反应的最适宜pH为8.0～8.5。     

Phosphorus removal by adsorbent based on poly-aluminum chloride sludge

Phosphorus adsorption tests were carried out using poly-aluminum chloride sludge (PACS), which was collected from a water treatment plant in Nanjing. The amount of phosphorus adsorbed by PACS increased quickly within the first hour and reached equilibrium after about 48 h. The adsorption behavior of PACS for phosphorus is consistent with the Langmuir adsorption isotherm equation (R² > 0.99) and parallel first-order kinetic equation (R² > 0.98). With the increase of the PACS concentration, the adsorption capacity of PACS for phosphorus decreased, and the removal rate increased. The results of batch tests showed that the adsorption capacities of PACS for phosphorus ranged from 1.64 to 1.13 mg/g when the pH value varied from 4 to 10. However, the adsorption capacity of PACS was not evidently influenced by temperature. In comparison with the ion exchange resin, the adsorption capacity of PACS was barely inhibited by competitive ions, such as ${\text{SO}}_4^{2-}$, ${\text{NO}}_3^{-}$, and Cl⁻. The PACS surface after adsorption became smooth, and the vibration peaks of Al–O and Al–OH shifted. Both HCl and NaOH have a strong desorption effect on PACS after adsorption saturation, and with higher concentrations of HCl and NaOH, the desorption effect was stronger. Results of column adsorption experiments showed that with lower phosphorus and hydraulic loads, the adsorption column took longer to reach saturation. This indicated that PACS could be used as an efficient material for removal of phosphorus from water. This study provides a new treatment method with PACS.     

Removal of lead(II) and copper(II) from aqueous solution using foitite from Linshou mine in Hebei, China

Foitite from Linshou mine in China's Hebei province was investigated as an adsorbent to remove Pb(II) and Cu(II) from aqueous solution. The results showed that foitite can readily remove heavy metal ions from aqueous solution. The data shows that the metal uptake for Pb(II) increases rapidly, accounting for 74.47% when contact time was 2 min. In contrast to Pb(ll), there was a worse capability for adsorption of Cu(II). In the first 4 min, the metal uptake accounted for 34.7%. According to the analytical results obtained from X-ray diffraction, laser Raman spectrum, X-ray energy dispersive spectrometer, and Zeta potential, the removal mechanism of Pb(II) and Cu(II) by using foitite can be explained as following: firstly, the existence of an electrostatic field around foitite particles can attract heavy metal ions and consequently combine heavy metal ions with OH; secondly, heavy metal ions in the solution are exchanged with the Fe3+ and Al3+ in the foitite.     

Evaluation of heavy metal inhibition of activated sludge by TTC and INT-electron transport system activity tests.

TTC and INT-electron transport system activity tests were compared for assessing heavy metal inhibition of activated sludge. The median inhibitory concentrations (IC50s) of Cu2+, Zn2+, Cd2+, Hg2+, Ni2+, Pb2+ and Ag+ measured via TTC test were lower than those measured via INT test, which indicates that the INT-electron transport system activity test was less sensitive to heavy metal toxicity than the TTC test. Tested heavy metals brought about similar decrease in TTC-electron transport system activity and COD removal rate, but less decrease in INT-electron transport system activity than COD removal rate, which suggests that the TTC-electron transport system activity is a better parameter for reflecting heavy metal inhibition of activated sludge than INT-electron transport system activity. The ranking of tested heavy metals in order of decreasing toxicity based on TTC test was Hg2+, Cd2+, Cu2+, Ag+, Zn2+, Ni2+ and Pb2+, and the ranking based on INT test was Hg2+, Ag+, Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+.     

Comparative MCDM Analysis for AMD Treatment Method Selection

Robule Lake, located in Eastern Serbia, near the city of Bor, is being influenced by waste materials from mining activities. For the purification of water from Robule Lake, contaminated with various metal ions (Fe, Cu, Zn, Mn, Cd, Ni, etc.), acid mine drainage (AMD) treatment methods such as: passive treatment method, sequential neutralization, ion exchange, adsorption process based on low cost adsorbents, adsorption process based on natural zeolits, electrodialysis, filtration with nanofiltration membranes, and reverse osmosis, were evaluated by the following MCDM methods: TOPSIS, VIKOR, MOOSRA, WASPAS, and CoCoSo. Criteria used for the evaluation were: efficiency in the metal ions removal and the quality of the purified water, necessity of pre-treatment and / or post-treatment of treated water, possibility of using the generated waste, capital costs, operating and maintenance costs, needed area, and sensitivity of the method. The results of the MCDM analysis showed that sequential neutralization was the most appropriate method for this wastewater, while passive treatment system and ion exchange were ranked as second and third, respectively.

After the selection of AMD treatment method, neutralization tests with lime were carried out with the water sample from Robule Lake. The results of sequential neutralization testing showed that concentration of Fe ions could be lowered to 1 mg/L at pH 4. The values of Cu, Zn, and Ni ions concentration obtained at pH 7 were 0.04, 0.65, and 0.21 mg/L, respectively, while the values of Mn and Cd ions concentration of 0.01 and 0.0001 mg/L, were obtained at pH 10.

     

Biological treatment of heavy metals in acid mine drainage using sulfate reducing bioreactors.

The uncontrolled release of acid mine drainage (AMD) from abandoned mines and tailing piles threatens water resources in many sites worldwide. AMD introduces elevated concentrations of sulfate ions and dissolved heavy metals as well as high acidity levels to groundwater and receiving surface water. Anaerobic biological processes relying on the activity of sulfate reducing bacteria are being considered for the treatment of AMD and other heavy metal containing effluents. Biogenic sulfides form insoluble complexes with heavy metals resulting in their precipitation. The objective of this study was to investigate the remediation of AMD in sulfate reducing bioreactors inoculated with anaerobic granular sludge and fed with an influent containing ethanol. Biological treatment of an acidic (pH 4.0) synthetic AMD containing high concentrations of heavy metals (100 mg Cu(2+)l(-1); 10 mg Ni(2+)l(-1), 10 mg Zn(2+)l(-1)) increased the effluent pH level to 7.0-7.2 and resulted in metal removal efficiencies exceeding 99.2%. The highest metal precipitation rates attained for Cu, Ni and Zn averaged 92.5, 14.6 and 15.8 mg metal l(-1) of reactor d(-1). The results of this work demonstrate that an ethanol-fed sulfidogenic reactor was highly effective to remove heavy metal contamination and neutralized the acidity of the synthetic wastewater.     

应用非参数的MK和ITA方法分析地下水水质参数变化特征——以新三矿含水层为例

矿区地下水水质变化是影响矿区生态环境和矿井安全生产的制约因素之一,正确认识水质变化趋势是首要任务。根据以往实测水质参数pH、COD、Na~++K~+、Ca~(2+)、Mg~(2+)、Cl~-、SO_4~(2-)和HCO_3~-的数据,采用Mann-Kendall检验法(MK)和Innovative Trend Analysis(ITA)探讨新三矿由上而下6个不同含水层水质参数随时间的演变规律,并且针对不同的数值变化范围选用不同的ITA指数。通过比较,两种方法结果有很好的一致性,结论认为:相比MK检测法,定量的ITA法拥有更多的优点,可以图形化地表示分析结果,可以通过将水质参数值分为低、中、高水平更好地分析水质参数的趋势和次要趋势;8种水质参数中,Ca~(2+)和Mg~(2+)相较其他离子能表现出更显著的变化趋势;6种含水层中,大青灰岩含水层中Cl~-浓度的低、中值下降而高值上升,煤层顶板山西组砂岩含水层和底板奥陶系灰岩含水层大部分水质参数显著下降,矿化度逐渐降低。     

Development of chitosan-based granular adsorbents for enhanced and selective adsorption performance in heavy metal removal.

Novel chitosan-based granular adsorbents were developed for enhanced and selective separation of heavy metal ions. The research included the synthesis of chitosan hydrogel beads, the cross-linking of the hydrogel beads with ethylene glycol diglycidyl ether (EGDE) in a conventional and a novel amine-shielded method, the functionalization of the chitosan beads through surface grafting of polyacrylamide via a surfaceinitiated atom transfer radical polymerization (ATRP) method, and the examination of the adsorption performance of the various types of chitosan beads in the removal of heavy metal ions. It was found that chitosan beads were effective in heavy metal adsorption, the conventional cross-linking method improved the acidic stability of the beads but reduced their adsorption capacity, the novel amine-shielded cross-linking method retained the good adsorption capacity while it improved the acidic stability of the beads, and the grafting of polyacrylamide on chitosan beads not only enhanced the adsorption capacity but also provided the beads with excellent selectivity for mercury over lead ions. XPS analyses indicated that the adsorption of metal ions on chitosan beads was mainly attributed to the amine groups of chitosan, the novel amine-shielded cross-linking method preserved most of the amine groups from being consumed by the cross-linking process and hence improved the adsorption capacity of the cross-linked chitosan beads, and the many amide groups from the polyacrylamide grafted on the chitosan beads increased the adsorption capacity and also made possible selective adsorption of mercury ions because the amide groups can form covalent bonds with mercury ions.     

Study on risk management of heavy metals for reuse of biosolids.

The behaviour of heavy metals was investigated at 22 wastewater treatment plants (WWTPs). In addition, the survey of heavy metal balance was conducted in detail at one WWTP. For the measurement, 22 types of heavy metals were selected from the chemical materials of pollutant release and transfer register (PRTR). There were some heavy metals, which were detected not in wastewater but in dewatered sludge. By means of the detailed survey at one WWTP, 60 to 80% of some heavy metals, such as B, Mn, Co, Ni and Mo, were discharged with treated water. According to the results of PRTR, Zn, B and Mn accounted for a large part of the discharge into the water course. To estimate the behaviour of heavy metals in the environment, leaching tests were applied to the products made of biosolids. During a series of leaching tests for building materials, it was observed that the concentration of heavy metals was very small, but the ratio of increase keeps a constant value. Therefore, it was considered that the acid extractable contents of heavy metal would be important.