Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium [Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.     

Removal of Cu(II) from aqueous solution in a fluidized-bed reactor

In this study, a fluidized-bed reactor (FBR) was employed to treat copper-containing wastewater by mean of copper precipitation on the surface of sand grains. The conditions for optimum copper removal efficiency were also investigated. This technology was controlled so as to keep supersaturation low to induce the nucleated precipitation of copper coating on the sand surface in an FBR. The effects of relevant parameters, such as the pH value, the molar ratio of [C(T)] to [Cu(2+)], hydraulic loading and the types of chemical reagents used, were examined. The experimental results indicated that 96% copper removal efficiency could be achieved when the influent copper concentration was 10mg l(-1). The optimum chemical reagent was Na(2)CO(3); the molar ratio of [C(T)]/[Cu(2+)] was 2, and the optimal hydraulic loading was not be more than 25m h(-1). In addition, preventing homogeneous nucleation in the FBR was an important operation parameter. Homogeneous nucleation and molecular growth would lead to undesirable microparticle formation in the effluent. A good mixture of carbonate and copper in the presence of sand grains could reduce the level of homogeneous nucleation in the bottom of the reactor. Energy dispersive analysis (EDS) of X-rays provided insight into the copper coating on the sand surface, and element analysis indicated the weight percentages of CuCO(3) and Cu(OH)(2) in precipitate.     

Copper activity in soil solutions of calcareous soils

Copper partitioning was studied in seven calcareous soils at moisture content corresponding to 1.2 times the field moisture content (soil water potential 7.84 J kg(-1)). Copper retention was accompanied by the release in soil solution of Ca(2+), Mg(2+), Na(+), and H(+), and the total amount of these cations released was 0.8 to 1.09 times the amount of Cu sorbed (mol(c):mol(c)). The relationships between Cu activity and pH, and the balance of cations in soils correspond with the surface precipitation of CuCO(3) as the main mechanism of Cu retention. The values of ion activity product of surface precipitate were close for all studied soils with the average log(IAP(CuCO(3)))=-15.51. The relationship between copper activity in soil solutions and soil properties is well fit by a regression relating pCu (-log copper ion activity) with soil pH, total Cu, and carbonate content.     

线路板园区综合废水碱法除铜优化实验

线路板废水中的铜主要以络合态存在,破络除铜是其处理稳定达标的关键环节。为了降低运行费用和产泥量,同时为后期的工程升级改造提供依据和参考,实验研究了碱法破络除铜最佳pH值、Na2S/Cu摩尔比、反应时间和絮凝剂种类的选择等,并从处理效率、投药成本、污泥产量多方面考核,确定最佳运行条件:以NaOH调节pH到10.5左右,Na2S与进水总铜摩尔比为1.5∶1～2∶1,反应30 min,再加100 mg/L的PAC和3 mg/L的PAM混凝反应,沉淀0.5 h,出水铜浓度低于0.3 mg/L,达到《电镀污染物排放标准》(GB 21900-2008)中的总铜排放标准。     

Use of activated dry flowers (ADF) of Alstonia Scholaris for chromium (Vl) removal: equilibrium, kinetics and thermodynamics studies

In this study, a natural adsorbent (activated dry flowers (ADF)) was prepared from plant-derived waste biomass by chemical activation and employed for chromium (VI) removal from aqueous medium using experimental batch technique. Experiments were carried out as function of adsorbent dosage, pH, and contact time. The maximum chromium (Vl) removal was observed at initial pH 3 (~94 % removal). The equilibrium data was fitted well to Langmuir isotherm. The adsorption capacity of ADF was found to be 4.40 (mg chromium (Vl)/g) which was comparable to the adsorption capacity of some other adsorbents documented. Among various kinetic models applied, pseudo second-order model was found to explain the kinetics of chromium (VI) adsorption most effectively (R ² >0.99). Thermodynamic parameters such as ΔG, ΔS, and ΔH shows that adsorption process was spontaneous and endothermic at all the concentration ranges studied. Desorption of chromium (Vl) with 2 N NaOH was effective (~71 %) and, hence, there exists the possibility of recycling the ADF. The major advantages of using ADF as an adsorbent are due to its effectiveness in reducing the concentration of chromium (Vl) to very low levels. It requires little processing and is reversible as well as eco-friendly in contrast to traditional methods.     

In situ immobilization of Cu(II) in soils using a new class of iron phosphate nanoparticles

This study tested the feasibility of using a new class of iron phosphate (vivianite) nanoparticles synthesized using sodium carboxymethyl cellulose (NaCMC) as a stabilizer for in situ immobilization of Cu(II) in soils. Transmission electron microscopy measurements demonstrated that the particle size was about 8.4+/-2.9 nm. Batch tests showed that nano-sized vivianite particles can effectively reduce the leachability and in vitro bioaccessibility of Cu(II) in three representative soils (calcareous, neutral, and acidic) at the low doses of 0.61 and 3.01 mg PO(4) g(-1) soil. The Cu leachability was evaluated by the toxicity characteristic leaching procedure and in vitro bioaccessibility was evaluated by the physiological based extraction test. In the case of soil amendment with nanoparticles in 3.01 mg PO(4) g(-1) soil, Cu leachability reduced 63-87% and Cu concentrations in TCLP extract decreased from 1.74-13.33 mg l(-1) to 0.23-2.55 mg l(-1) after those soils were amended for 56 d. Meanwhile, the bioaccessibility of Cu was reduced by 54-69%. Sequential extraction procedures showed the significant decrease of water soluble/exchangeable Cu(II) and carbonate bound fractions and concomitant increase of Cu residual fraction after the soils were amended with the nanoparticles, suggesting that the formation of copper phosphate minerals through precipitation and adsorption was probably responsible for the decrease of Cu availability in soils. Visual MINTEQ modeling further revealed that Cu(3)(PO(4))(2) and Cu(5)(PO(4))(3)OH were formed in the vivianite-solid Cu(II) system, resulting in the decreased solubility of the Cu(II) in the acidic pH range.     

Recycling EDTA solutions used to remediate metal-polluted soils

The objective of this research was to investigate the recycling of ethylenediamine-tetraacetic acid (EDTA) used for the removal of trace metals from contaminated soils. We successfully used Na2S combined with Ca(OH)2 to precipitate the trace metals allowing us to recycle the EDTA. The results of batch and column leaching experiments show that both Ca-EDTA and Na-EDTA are powerful chelating agents with a similar soil remediation potential. The major advantage of Ca-EDTA is the preservation of soil organic matter. We found that Na2S was capable of separating the metals Cd, Cu and Pb from EDTA; however, the precipitation of Zn required the addition of Ca(OH)2. After reusing the reclaimed EDTA seven times, over a 14-day period, EDTA reagent losses ranged from 19.5% to 23.5%. Successive washing cycles enhanced the removal of trace metals from contaminated soils. The metal sulfide precipitates contain high concentrations of metals and could potentially be recycled.     

Waste Fe(III)/Cr(III) hydroxide as adsorbent for the removal of Cr(VI) from aqueous solution and chromium plating industry wastewater

Fe(III)/Cr(III) hydroxide, a waste material from the fertilizer industry, has been used for the adsorption of Cr(VI) from aqueous solution, over a range of initial metal ion concentrations (5-30 mg litre(-1)), agitation times (1-180 min), adsorbent dosages (100-1200 mg per 50 ml), temperatures (24, 29 and 38 degrees C) and pH values (4.5-10). The adsorption of Cr(VI) increased with the initial concentration of Cr(VI) and with temperature. The process of uptake follows both the Langmuir and the Freundlich isotherm models. The applicability of Lagergren and empirical kinetic models has also been investigated. Almost quantitative removal of Cr(VI) at 10 mg litre(-1) in a 50-ml solution by 500 mg of adsorbent was found at an equilibrium pH of 5.6. The efficiency of chromium removal was also tested using wastewater from the chromium plating industry.     

Adsorption of Acid Red 73 on copper dithiocarbamate precipitate-type solid wastes

Three solid wastes, copper N,N'-bis(dithiocarboxy)piperazine ([CuBDP](n)), copper diethyldithiocarbamate (Cu(DDTC)(2)) and copper dimethyldithiocarbamate (Cu(DMTC)(2)), were prepared and tested as adsorbents to remove Acid Red 73 from wastewater. It was found that the three precipitates all could effectively adsorb the dye but their adsorption abilities were rather different. The maximum adsorption amounts of the coordination polymer precipitate [CuBDP](n) reached as high as 364mg g(-1), much greater than those of Cu(DDTC)(2) and Cu(DMTC)(2) (42.9 and 37.8mg g(-1), respectively). The investigation of adsorption models showed these adsorption processes followed the pseudo-second-order kinetic equation and the adsorption balances could be described with both Langmuir and Freundlich isotherms, but the latter seemed to be more suitable. Their adsorption nature was inferred to be physical adsorption and mainly depended on the hydrophobic interaction between these precipitates and Acid Red 73. This is the first example for the reutilization of metal dithiocarbamate precipitates as solid wastes to date.     

4A沸石对复合污染水体中Pb2+、Cu2+和Cd2+的去除

采用静态吸附法以4A沸石为吸附剂研究其对复合污染水体中Pb2+、Cu2+和Cd2+的竞争吸附特性,并探讨了影响吸附的环境因素。实验表明,在室温条件下,溶液pH5～6,4A沸石15 mg对10 mL复合污染溶液(Pb2+、Cu2+和Cd2+浓度分别为100 mg/L)吸附20 min时,对溶液中3种重金属的吸附去除率均可达99.8%以上。反应过程中4A沸石对3种重金属的吸附速率大小为Pb2+>Cu2+>Cd2+。复合污染水体中4A沸石对Pb2+、Cu2+和Cd2+的吸附符合Langmuir和Fre-undlich等温吸附方程,相关系数分别为0.9981、0.9901、0.9916和0.9638、0.9194、0.9689。经计算,4A沸石对Pb2+、Cu2+和Cd2+的饱和吸附量分别为129.9 mg/g、107.5 mg/g和99.0 mg/g。4A沸石吸附重金属离子达到吸附平衡的时间较短,对溶液pH值的适应性较好。吸附后的4A沸石可以再生利用,对铅离子洗脱重复利用性较铜离子和镉离子强。     

Modeling of electrodialytic and dialytic removal of Cr, Cu and As from CCA-treated wood chips

A one-dimensional model is developed for simulating the electrodialytic and dialytic treatment of a saturated bed of wood chips containing chromium, copper and arsenic. The movement of Cr, Cu and As is mathematically modeled taking into account the diffusion transport resulting from the concentration gradients of their compounds and the electromigration of their ionic, simple and complex species during the operation. The model also includes the electromigration of the non-contaminant principal ionic species in the system, H(+) and OH(-), proceeding from the electrolysis at the electrodes, Na(+) and NO(3)(-) used as electrolyte solutions in the electrode compartments, and oxalate ions and protons incorporated with the oxalic acid solution during wood chips incubation. The model simulation also takes into account that OH(-) generated on the cathode, during electrodialytic remediation, is periodically neutralized by addition of nitric acid in the cathode compartment. The anion and cation-exchange membranes are simply represented as ionic filters that preclude the transport of co-ions (the cations and anions respectively) with the exception of H(+), which is retarded but considered to pass through the anion-exchange membrane.     

土壤中无机钠盐对不同形态Cu含量的影响

采用TESSIER连续提取法研究了不同种类、不同加入量的无机钠盐对土壤中不同形态Cu含量的影响。结果表明,对于可交换态Cu,3种无机钠盐的加入均使其含量减少,其中NaCl的影响最大,4、8g/kg的NaCl分别使其减少了28.13%(质量分数,下同)和50.59%;对于碳酸盐结合态Cu,3种无机钠盐的加入均使其含量增加,其中Na2CO3(8g/kg)对其影响最大;对于铁锰氧化态Cu,Na2SO4和Na2CO3的加入使其含量先升高后降低,NaCl则使其含量降低;有机结合态Cu受Na2SO4和Na2CO3的影响较大,在它们的影响下含量均增加;残渣态Cu在3种无机钠盐的影响下变化幅度均很大,其中4、8g/kg的Na2SO4分别使其含量减少了47.47%和62.21%。     

Copper and trace element fractionation in electrokinetically treated methanogenic anaerobic granular sludge

The effect of electrokinetic treatment (0.15 mA cm(-2)) on the metal fractionation in anaerobic granular sludge artificially contaminated with copper (initial copper concentration 1000 mg kg(-1) wet sludge) was studied. Acidification of the sludge (final pH 4.2 in the sludge bed) with the intention to desorb the copper species bound to the organic/sulfides and residual fractions did not result in an increased mobility, despite the fact that a higher quantity of copper was measured in the more mobile (i.e. exchangeable/carbonate) fractions at final pH 4.2 compared to circum-neutral pH conditions. Also addition of the chelating agent EDTA (Cu2+:EDTA4- ratio 1.2:1) did not enhance the mobility of copper from the organic/sulfides and residual fractions, despite the fact that it induced a reduction of the total copper content of the sludge. The presence of sulfide precipitates likely influences the copper mobilisation from these less mobile fractions, and thus makes EDTA addition ineffective to solubilise copper from the granules.     

Chromium(VI) sorptive removal from aqueous solutions by nanocrystalline akaganèite

In this study, akaganeite (beta-FeO(OH)) an ironoxyhydroxide material, was used as a low-cost potential adsorbent for the removal of hexavalent chromium from aqueous solutions. The influence of agitation speed, solution pH, initial chromium concentration, sorbent concentration and temperature were evaluated at batch kinetic runs. It was shown that the solid diffusion model, in comparison to simple reaction kinetic models, described better the sorption kinetics. Freundlich and Frumkin isotherm best fitted the equilibrium results. Akaganeite presented a sorption capacity approximately 80 mg Cr(VI) g(-1), under the conditions studied. Flotation was used as a downstream process for the effective removal of the loaded material.     

Copper and cadmium removal from synthetic industrial wastewater using chitosan and nylon 6

Purpose

Chitosan with nylon 6 membranes was evaluated as adsorbents to remove copper and cadmium ions from synthetic industrial wastewater.

Methods

Chitosan and nylon 6 with glutaraldehyde blend ratio with (1:1+Glu, 1:2+Glu, and 2:1+Glu) have been prepared and these were used as membranes to remove copper and cadmium ions from synthetic industrial wastewater. Characterization of the synthesized membrane has been done with FTIR, XRD, TGA/DTA, DSC, and SEM. Chemical parameters for quantities of adsorption of heavy metal contamination have been done and the kinetics of adsorption has also been carried out.

Results

The optimal pH for the removal of Cd(II) and Cu(II) using chitosan with nylon 6. Maximum removal of the metals was observed at pH 5 for both the metals. The effect of adsorbent dose also has a pronounced effect on the percentage of removal of the metals. Maximum removal of both the metals was observed at 5 g/100 ml of the adsorbent.

Conclusion

Copper and cadmium recovery is parallel at all time. The percentage of removal of copper increased with increase in the pH from 3 to 5. In the case of cadmium containing wastewater, the maximum removal of metal occurred at pH 5. The uptake amount of Cu²⁺ ions on chitosan increased rapidly with increasing contact time from 0 to 360 min and then reaches equilibrium after 360 min; the equilibrium constant for copper and cadmium ions is more or less the same for the adsorption reaction.     

碳酸根对磷酸钙沉淀反应回收磷的影响

以模拟的厌氧消化液为处理对象,通过小试实验,考察不同初始磷浓度Cp、Ca／P物质的量比、pH和温度下,碳酸根（CO3 2-）对磷酸钙沉淀反应回收磷的影响;利用扫描电镜（SEM）、x射线衍射仪（XRD）和傅里叶变换红外光谱（FT．IR）对沉淀产物进行表征。结果表明,高浓度的CO3 2-对以磷酸钙沉淀反应去除和回收磷的效率影响较大;Cp相同时,CO3 2-浓度（CCO3^2-）越大,P的去除率越低,低C,（20mg／L）时尤为显著;当CCO3^2-相同时,随着Cp的增大,反应速率加快,P的去除率逐渐升高,但升高幅度越来越小;增大Ca／P比和pH能提高P的去除率,降低CO3 2-对磷酸钙沉淀反应的抑制作用,综合考虑实际效果,应选择Ca／P比为3．33,pH为9．0作为适宜的反应条件;升高温度对降低CO3 2-对磷酸钙沉淀反应的抑制作用贡献不大。在Cp为60ITIg／L,Ca／P比为1．67,pH为9．0,温度为20℃的条件下,当CCO3^2-为0时,得到的沉淀产物主要为羟基磷灰石HAP;当CCO3^2-为30mmol／L时,得到的沉淀产物为磷酸钙和碳酸合磷灰石的混合物。     

麻质活性炭的制备及其对Cu2＋的吸附研究

以废麻为原料,KOH为活化剂制备粉状活性炭,通过静态吸附实验研究了活性炭对Cu2＋的吸附性能,探讨了溶液起始pH值、活性炭投加量、吸附时间、起始Cu2＋质量浓度等对Cu2＋吸附效果的影响。结果表明,溶液pH和活性炭投加量对吸附效果有较大影响,活性炭对Cu2＋的吸附率在60 min内超过50%,初始浓度在10~50 mg/L时,活性炭对Cu2＋的吸附量与起始浓度近似成正比。采用Langmuir、Freundlich吸附等温式对吸附平衡数据进行了拟合,结果表明吸附等温线符合Frenudlich模型。采用傅立叶红外光谱法（FT-IR）分析了活性炭的表面官能团,分析表明活性炭表面酸性官能团可能是吸附Cu2＋的活性中心。     

Effect of fly ash characteristics on the removal of Cu(II) from aqueous solution

Fly ash is a particulate substance containing metal oxides, carbon and other microelements. In this study, fly ashes with different quantities of carbon and minerals prepared by a thermal process in the laboratory were used as adsorbents to investigate the contribution of precipitation and adsorption to the removal of aqueous Cu(II). Experimental results showed that the specific surface area of fly ash increased linearly with the quantity of carbon. The specific surface areas of the carbon and mineral fraction were 60 m2/g and 0.68 m2/g, respectively. The specific adsorption capacities of carbon ranged from 2.2 to 2.8 mg Cu/g carbon, while those for mineral were only about 0.63 to approximately 0.81 mg Cu/g mineral. Consequently, the carbon fraction in fly ash was important in the removal of Cu(II) at pH 5. However, Cu(II) removal owing to precipitation increases with a decreasing carbon fraction and the contribution of copper precipitation was estimated to be approximately 23% to approximately 82% of total removal, depending on the carbon fraction of fly ash.     

Toxicity of uranium and copper individually, and in combination, to a tropical freshwater macrophyte (Lemna aequinoctialis)

Copper (Cu) and uranium (U) are of potential ecotoxicological concern to tropical freshwater biota in northern Australia, as a result of mining activities. Few data are available on the toxicity of U, and no data are available on the toxic interaction of Cu and U, to freshwater biota. This study determined the toxicity of Cu and U individually, and in combination, to a tropical freshwater macrophyte, Lemna aequinoctialis (duckweed), in a synthetic soft water (27 degrees C; pH, 6.5; hardness, 40 mg CaCO3 l-1, alkalinity, 16 mg CaCO3 l-1), typical of many fresh surface waters in coastal northern Australia. The growth rate of L. aequinoctialis decreased with increasing Cu or U concentrations, with the concentration of Cu inhibiting growth by 50% (EC50) being 16+/-1.0 microg l-1, with a minimum detectable effect concentration (MDEC) of 3.2 microg l-1. The concentration of U inhibiting growth by 50% (EC50) was 758+/-35 microg l-1 with a MDEC of 112 microg l-1. The EC50 value for the exposure of L. aequinoctialis to equitoxic mixtures of Cu and U was significantly (P0.05) higher than one toxic unit (1.35; 95% confidence interval, 1.18-1.52), indicating that the combined effects of Cu and U are less than additive (antagonistic). Therefore, inhibition of the growth rate of L. aequinoctialis was reduced when Cu and U were present in equitoxic mixtures, relative to individual metal exposures. Since non-additive (e.g. antagonistic) interactions of metal mixtures cannot be predicted using current mixture models, these results have important potential implications for the protection of freshwater ecosystems through the derivation of national water quality guidelines.     

淀粉基黄原酸盐处理重金属废水的条件优化研究

采用淀粉基黄原酸盐处理含重金属的电镀废水 ,对淀粉基黄原酸盐的用量、pH值和反应时间等条件进行了研究。结果发现 ,1L含氰电镀废水 (含Cr3+15mg/L、Cu2 +3mg/L、Ni2 +9.2mg/L和Zn2 +6mg/L) ,加入 1g淀粉基黄原酸盐 ,调节 pH为 8,搅拌 1h ,过滤 ,处理后的废水中Cr3+、Cu2 +、Zn2 +和Ni2 +残余浓度分别为 0 .0 8mg/L、0 .0 1mg/L、0 .1mg/L和 0 .0 8mg/L。含有重金属盐的残渣 ,可用硝酸处理 ,以回收重金属