Study on the hydrolysis/precipitation behavior of Keggin Al13 and Al30 polymers in polyaluminum solutions

The hydrolysis/precipitation behaviors of Al³⁺, Al₁₃ and Al₃₀ under conditions typical for flocculation in water treatment were investigated by studying the particulates' size development, charge characteristics, chemical species and speciation transformation of coagulant hydrolysis precipitates. The optimal pH conditions for hydrolysis precipitates formation for AlCl₃, PAC_Al13 and PAC_Al30 were 6.5–7.5, 8.5–9.5, and 7.5–9.5, respectively. The precipitates' formation rate increased with the increase in dosage, and the relative rates were AlCl₃ ? PAC_Al30 > PAC_Al13. The precipitates' size increased when the dosage increased from 50 μM to 200 μM, but it decreased when the dosage increased to 800 μM. The Zeta potential of coagulant hydrolysis precipitates decreased with the increase in pH for the three coagulants. The iso-electric points of the freshly formed precipitates for AlCl₃, PAC_Al13 and PAC_Al30 were 7.3, 9.6 and 9.2, respectively. The Zeta potentials of AlCl₃ hydrolysis precipitates were lower than those of PAC_Al13 and PAC_Al30 when pH > 5.0. The Zeta potential of PAC_Al30 hydrolysis precipitates was higher than that of PAC_Al13 at the acidic side, but lower at the alkaline side. The dosage had no obvious effect on the Zeta potential of hydrolysis precipitates under fixed pH conditions. The increase in Zeta potential with the increase in dosage under uncontrolled pH conditions was due to the pH depression caused by coagulant addition. Al–Ferron research indicated that the hydrolysis precipitates of AlCl₃ were composed of amorphous Al(OH)₃ precipitates, but those of PAC_Al13 and PAC_Al30 were composed of aggregates of Al₁₃ and Al₃₀, respectively. Al³⁺ was the most un-stable species in coagulants, and its hydrolysis was remarkably influenced by solution pH. Al₁₃ and Al₃₀ species were very stable, and solution pH and aging had little effect on the chemical species of their hydrolysis products. The research method involving coagulant hydrolysis precipitates based on Al–Ferron reaction kinetics was studied in detail. The Al species classification based on complex reaction kinetic of hydrolysis precipitates and Ferron reagent was different from that measured in a conventional coagulant assay using the Al–Ferron method. The chemical composition of Al_a, Al_b and Al_c depended on coagulant and solution pH. The Al_b measured in the current case was different from Keggin Al₁₃, and the high Al_b content in the AlCl₃ hydrolysis precipitates could not used as testimony that most of the Al³⁺ was converted to highly charged Al₁₃ species during AlCl₃ coagulation.     

Combined use of molecular biology taxonomy, Raman spectrometry, and ESEM imaging to study natural biofilms grown on filter materials at waterworks

DNA-based population analysis was applied in combination with Raman spectrometry and Environmental Scanning Electron Microscopy for the characterisation of natural biofilms from sand and activated carbon filters operated for a long term at a municipal waterworks. Whereas the molecular biology polymerase chain reaction combined with denaturing gradient gel electrophoresis approach provides a deeper insight into the bacterial biofilm diversities, Raman spectrometry analyses the chemical composition of the extracellular polymer substances (EPS), microorganisms embedded in EPS as well as other substances inside biofilm (inorganic compounds and humic substances). Microscopy images the spatial distribution of biofilms on the two different filter materials. In addition, bacterial bulk water populations were compared with biofilm consortia using the molecular fingerprint technique mentioned.Population analysis demonstrated the presence of more diverse bacterial species embedded in a matrix of EPS (polysaccharides, peptides, and nucleic acids) on the sand filter materials. In contrast to this, activated carbon granules were colonised by reduced numbers of bacterial species in biofilms. Besides α-, β-, and γ-Proteobacteria, a noticeable specific colonisation with Actinobacteria was found on activated carbon particles. Here, the reduced biofilm formation came along with a decreased EPS synthesis. The taxonomy profiles of the different biofilms revealed up to 60% similarity on the same filter materials and 32% similarity of different materials. Similarity of adherent communities from filter materials and bulk water populations from the filter effluent varied between 36% and 58% in sand filters and 6–40% in granular activated carbon filters.The biofilm investigation protocols are most crucial to subsequent acquisition of knowledge on biofilm dynamics and bacterial contributions to transformation or adsorption processes in waterworks facilities.     

Part V—sorption of pharmaceuticals and personal care products

Background, aim, and scope  Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. Main features  We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP–soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)–mineral–water). The complexity of three-phase systems was also discussed. Results  Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Discussion  Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical–physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Conclusions  Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. Recommendations and perspectives  More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.     

Effects of acute γ-irradiation on the aquatic microbial microcosm in comparison with chemicals

Effects of acute γ-irradiation were investigated in the aquatic microcosm consisting of green algae (Chlorella sp. and Scenedesmus sp.) and a blue–green alga (Tolypothrix sp.) as producers; an oligochaete (Aeolosoma hemprichi), rotifers (Lecane sp. and Philodina sp.) and a ciliate protozoan (Cyclidium glaucoma) as consumers; and more than four species of bacteria as decomposers. At 100 Gy, populations were not affected in any taxa. At 500–5000 Gy, one or three taxa died out and populations of two or three taxa decreased over time, while that of Tolypothrix sp. increased. This Tolypothrix sp. increase was likely an indirect effect due to interspecies interactions. The principal response curve analysis revealed that the main trend of the effects was a dose-dependent population decrease. For a better understanding of radiation risks in aquatic microbial communities, effect doses of γ-rays compared with copper, herbicides and detergents were evaluated using the radiochemoecological conceptual model and the effect index for microcosm.     

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

Fluoride removal by a continuous flow electrocoagulation reactor

Long-term consumption of water containing excessive fluoride can lead to fluorosis of the teeth and bones. Electrocoagulation (EC) is an electrochemical technique, in which a variety of unwanted dissolved particles and suspended matter can be effectively removed from an aqueous solution by electrolysis. Continuous flow experiments with monopolar aluminium electrodes for fluoride removal were undertaken to investigate the effects of the different parameters such as: current density (12.5-50A/m(2)), flow rate (150-400 mL/min), initial pH (4-8), and initial fluoride concentration (5-25mg/L). The highest treatment efficiency was obtained for the largest current and the removal efficiency was found to be dependent on the current density, the flow rate and the initial fluoride concentration when the final pH ranged between 6 and 8. The composition of the sludge produced was analysed using the X-ray diffraction (XRD) spectrum. The strong presence of the aluminium hydroxide [Al(OH)(3)] in the above pH range, which maximizes the formation of aluminium fluoride hydroxide complex [Al(n)F(m)(OH)(3n-m)], is the main reason for defluoridation by electrocoagulation. The results obtained showed that the continuous flow electrocoagulation technology is an effective process for defluoridation of potable water supplies and could also be utilized for the defluoridation of industrial wastewater.     

纳米光催化氧化测定不同水体化学需氧量的研究

采用简便的沉淀法制备的纳米氧化锌为光催化荆,重铬酸钾为光生电子接受体,研究了纳米氧化锌-重铬酸钾体系测定COD的方法.COD值在1～100mg/L之间有良好的线性关系,线性方程为y=0.0007χ 0.0069,相关系数为r=0.9992,检测限为0.66mg,L.采用本方法和CODM.国标法对不同水体样品进行比较测定发现,对低COD值样品本方法加标回收率在96.3%～100.6%之间,变异系数Cv%=1.1～3.4,准确度和精密度均优于CODMn国标法,弥补了低COD值样品国标法(CODmn)测定不准确的不足,且单个样品测定时间短,具有推广应用价值.     

细菌在近海污染监测及评价中的应用研究

通过对天津渤海湾的三个河流入海口(青静黄排水河、独流减河和海河),不同季节实地采集的水样中微生物数量及理化因子如温度、盐度、溶解氧(DO)、化学需氧量(COD)、无机氮等的研究,发现细菌指标与理化指标对污染指示结果有一定的相似性,都指示青静黄排水河河口污染较严重.利用SPSS软件的相关性分析方法对实验结果进行分析,发现水环境中细菌指标与理化因子具有一定的相关性.其中异养菌数与COD呈显著正相关性(P<0.05),与DO呈负相关性(P=0.051);大肠菌群数与理化因子DO呈极显著负相关关系(P<0.01),与COD呈正相关关系(P=0.061),与NO3-N,盐度呈负相关性(P>0.05).其他细菌指标与各理化因子也存在一定的相关性,但不明显.     

Extension of the EUROS Integrated Air Quality Model to Fine Particulate Matter by Coupling to CACM/MADRID 2

The European Operational Smog (EUROS) integrated air quality modelling system has been extended to model fine particulate matter (PM). From an extended literature study, the Caltech Atmospheric Chemistry Mechanism and the Model of Aerosol Dynamics, Reaction, Ionisation and Dissolution were selected and recently coupled to EUROS. Currently, modelling of mass and chemical composition of aerosols in two size fractions (PM_2.5 and PM_10–2.5) is possible. The chemical composition is expressed in terms of seven components: ammonium, nitrate, sulphate, elementary carbon, primary inorganic compounds, primary organic compounds and secondary organic compounds. Calculated PM₁₀ concentrations and chemical composition are presented for two summer months of the year 2003 (1 July to 31 August).     

江苏沿江某化工园区有机污染调查与研究

选择沿江某典型化工园区进行有机污染调查分析,分析污染排放特征及其对长江水质影响.为了解工业园区环境污染状况、从源头控制有机毒物等提供科学依据.