Leaching behavior of Pb and Zn in air pollution control residues and their modeling prediction

Increasing attention has been paid to air pollution control （APC） residues in China recently due to the rising proportion of waste incineration and the hazardous characteristics of the residues, among which heavy metal leaching toxicity plays an important role. Leaching behavior and potential risk of Pb and Zn in the APC residues from a Shanghai municipal solid waste （MSW） incinerator was studied, based on the leaching tests under different conditions and theoretical calculation using a geochemical thermodynamic equilibrium model MINTEQA2. Results showed that, extractant species and liquid to solid （L/S） ratio predominantly controlled the leaching toxicity of Pb and Zn, while ionic strength, vibration method and leaching time had less effect on the metals release. Leachate/final pH determined the metal leaching behavior, which changed the speciation of heavy metals in the extraction system. The equilibrium aqueous speciation, precipitation-dissolution of Pb and Zn was investigated according to the model computation, which was well in agreement with the experimental results.

Study on Management and Control of Nonpoint Source Pollution from Urban Surface Runoff

Urbanization is the dominant form of land-use change in terms of impacts on water quality, hydrology, physical proper- ties of watersheds and their nonpoint source (NPS) pollution po- tential at present. Urbanization has changed the source, process and sink of urban NPS pollution, especially raised the pollution load of urban runoff NPS in receiving water. Urban runoff pollu- tion is a hot spot of research on NPS. This paper analyzed type, source and harm of the NPS pollutants of urban runoff and its influence on the receiving water. Through estimating NPS pollu- tion load of urban runoff and summarizing the law and character- istics of urban runoff NPS systemically, study on management and control of urban runoff NPS pollution was focused on the applica- tion of BMPs (best management practices). It is a fresh method- ology that management and control on NPS pollution from urban surface runoff was analyzed by methods of landscape ecology, environmental economics and environmental management. The paper provided a scientific reference for mitigating urban water environment pressure and an effective method for management and control of NPS pollution from urban surface runoff..

Effects of ultrasonic pretreatment on sludge dewaterability and extracellular polymeric substances distribution in mesophilic anaerobic digestion

Effect of ultrasonic pretreatment on sludge dewaterability was determined and the fate of extracellular polymeric substances （EPS） matrix in mesophilic anaerobic digestion after ultrasonic pretreatment was studied. Characteristics of proteins （PN）, polysaccharides （PS）, excitation-emission matrix （EEM） fluorescence spectroscopy and molecular weight （MW） distribution of dissolved organic matters （DOM） in different EPS fractions were evaluated. The results showed that after ultrasonic pretreatment, the normalized capillary suction time （CST） decreased from 44.4 to 11.1 （sec·L）/g total suspended solids （TSS） during anaerobic digestion, indicating that sludge dewaterability was greatly improved. The normalized CST was significantly correlated with PN concentration （R2 = 0.92, p 〈 0.01） and the PN/PS ratio （R2 = 0.84, p 〈 0.01） in the loosely bound EPS （LB-EPS） fraction. Meanwhile, the average MW of DOM in the LB- EPS and tightly bound EPS （TB-EPS） fractions also had a good correlation with the normalized CST （R2 〉 0.66, p 〈 0.01）. According to EEM fluorescence spectroscopy, tryptophan-like substances intensities in the slime, LB-EPS and TB-EPS fractions were correlated with the normalized CST. The organic matters in the EPS matrix played an important role in influencing sludge dewaterability.

Changes of Cu, Zn, and Ni chemical speciation in sewage sludge co-composted with sodium sulfide and lime

A batch composting study was performed to evaluate the feasibility of co-composting sewage sludge with sodium sulfide and lime （SSL） mixture （Na2S/CaO= 1：1）, aiming at reducing the availability of heavy metals in the sludge compost. Sewage sludge with sawdust as a bulking agent was amended with SSL at 3% （w/w, dw）, and composted for 15 d in laboratory batch reactors. The four stages of the Tessier sequential extraction method was employed to investigate changes in heavy metal fractions of Cu, Zn, and Ni in sewage sludge composted with SSL. For all the three metals, the mobile fractions, such as, exchangeable and carbonate bound were mainly transformed into low availability fractions （organic matter and sulfide, Fe-Mn oxides bound and residual forms）, and the addition of SSL enhanced this transformation. Therefore, SSL is a suitable material to co-compost with sewage sludge to reduce the availability of heavy metals. According to the cabbage seed germination test, a SSL amendment of ≤3% （w/w, dw） is recommended to co-compost with sewage sludge.

Biosorption of cadmium(II) and lead(II) ions from aqueous solutions onto dried activated sludge

The removal of heavy-metal ions from aqueous solutions by using dried activated sludge has been investigated in batch systems. Effect of solution pH, initial metal ion concentration, and temperature were determined. The results of the kinetic studies showed that the uptake processes of the two metal ions（Cd（Ⅱ） and Pb（Ⅱ）） followed the pseudo-second-order rate expression. The equilibrium data fitted very well to both the Langmuir and Freundlich adsorption models. The FT-IR analysis showed that the main mechanism of Cd（Ⅱ） and Pb（Ⅱ） biosorption onto dried activated sludge was their binding with amide I group.

Three-stage aged refuse biofilter for the treatment of landfill leachate

A field-scale aged refuse （AR） biofilter constructed in Shanghai Refuse Landfill, containing about 7000 m^3 aged refuse inside, was evaluated for its performance in the treatment of landfill leachate. This AR biofilter can be divided into three stages and can manage 50 m^3 landfill leachate per day. The physical, chemical, and biological characteristics of AR were analyzed for evaluating the AR biofilter as leachate treatment host. The results revealed that over 87.8%-96.2% of COD and 96.9%-99.4% of ammonia nitrogen were removed by the three-stage AR biofilter when the infiuent leachate COD and ammonia nitrogen concentration were in the range 5478-10842 mg/L and 811-1582 mg/L, respectively. The final effluent was inodorous and pale yellow with COD and ammonia nitrogen below 267-1020 mg/L and 6-45 mg/L, respectively. The three-stage AR biofilter had efficient nitrification but relative poor denitrification capacity with a total nitrogen （TN） removal of 58%-73%. The external temperature of AR biofilter did not influence the total ammonia nitrogen removal significantly. It was concluded that the scale-up AR biofilter can work very well and can be a promising technology for the treatment of landfill leachate.

Semivolatile organic compounds, organochlorine pesticides and heavy metals in sediments and risk assessment in Huaihe River of China

The concentrations of semivolatile organic compounds, organochlorine pesticides and heavy metals in sediments from Jiangsu reach of Huaihe River, China, were presented. The organic compounds were extracted by acetone： n-hexane using a Soxhlet apparatus and concentrations were performed using HP6890 gas chromatography coupled by FID and ECD detector. The total contents of 8 heavy metals by inductively coupled plasma atomic emission spectrometry or cold-vapor/atomic absorption spectrometry were developed. 30 semivolatile organic compounds were detected, including substituted benzenes, phenols, phthalates and polycyclic aromatic hydrocarbons, from 0.01 to 3.01 mg/kg. 16 organochlorine pesticides were almost detected and from 0.010 to 2.339 μg/kg. Concentrations of major metals were 50 mg/kg or less, mean level of mercury was only 0.055 mg/kg. Compared to sediment quality guidelines （SQGs）, concentrations of some semivolatilc organic compounds were high enough to cause possible toxic effects to living resources. The organochlorine pesticides presented relatively low, lower than threshold effect concentrations （TECs）, harmful effects on sediment-dwelling organisms were not expected. Chromium posed probable toxic effects to the living resources, other heavy metals had no threat temporarily according to SQGs.

Isolates identification and characteristics of microorganisms in biotrickling filter and biofilter system treating H_2S and NH_3

A combination system of biotrickling filter （BTF） and biofilter （BF）, adopting surfactant-modified clinoptilolite and surfactant- modified wood chip as the media respectively, was applied to treat H2S and NH3 simultaneously. The identification and sole carbon sources utilization patterns of isolates in the combination system were studied by Biolog system. The isolates were identified as Bacillus sphaericus, Geobacillus themoglucosidasius （55℃） and Micrococcus luteus （ATCC 9341） in BTF, and Aspergillus sydowii （Bainier ＆ Sartory） Thom＆ Church in BE Among 95 substrate classes supplied by Biolog system, the carboxylic acids and methyl esters had the highest utilization extent for the four species, followed by the amino acids and peptides. The descending sequence of carbon sources utilization capability of isolates was A. sydowii （52.6%）, M. luteus （39.5%）, B. sphaericus （21.6%）, and G. thermoglucosidasius （17.7%）.

ADSORPTION OF CHLOROFORM AND TRICHLOROETHYLENE IN WATER WITH A NEW KIND OF HYPERCROSSLINKED RESINS

In this paper two newly developed hypercrosslinked resins were used to treat micropolluted drinking water and their static and kinetic adsorption were investigated at 293 K. The results show that these two adsorbents are superior to Amberlite XAD-4 for removing chloroform and trichloroethylene in aqueous solutions. The breakthrough capacity and the total capacities from mini-column adsorption studies for chloroform and trichloroethylene on XAD-4, ZH-01 and ZH-00 are calculated respectively under experimental conditions

Adsorption thermodynamics and kinetic investigation of aromatic amphoteric compounds onto different polymeric adsorbents

The adsorption behavior ofp-aminobenzoic acid and o-aminobenzoic acid onto the different polymeric adsorbents was systematically investigated as a function of the solution concentration and temperature. Experimental results indicated that the equilibrium adsorption data of the four polymeric adsorbents fitted well in the Freundlich isotherm. The adsorption capacity of multi-functional polymeric adsorbent NJ-99 was the highest, which might be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of aminobenzoic acid. The adsorption capacity of o-aminobenzoic acid onto any adsorbent was higher than p-aminobenzoic acid. Thermodynamic studies suggested the exothermic, spontaneous physical adsorption process. Adsorption kinetics results showed that the adsorption followed the pseudo-second-order kinetics model and the intraparticle mass transfer process was the rate-controlling step.

Aerobic biodegradation of di-n-butyl phthalate by Xiangjiang River sediment and microflora analysis

Di-n-butyl phthalate (DBP),one of phthalate acid esters (PAEs),was investigated to determine its biodegradation rate using Xiangjiang River sediment and find potential DBP degraders in the enrichment culture of the sediment. The sediment sample was incubated with an initial concentration of DBP of 100 mg/L for 5 d. The biodegradation rate of DBP was detected using HPLC and the degraded products were analyzed by GC/MS. Subsequently,the microbial diversity of the enrichment culture was analyzed by polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP). The results reveal that almost 100% of DBP is degraded after merely 3 d,generating two main degraded products:mono-butyl phthalate (MBP) and 9-octadecenoic acid. After a six-month enrichment period under the pressure of DBP,the dominant family in the final enrichment culture is clustered with the Comamonas sp.,the remaining are affiliated with Sphingomonas sp.,Hydrogenophaga sp.,Rhizobium sp.,and Acidovorax sp. The results show the potential of these bacteria to be used in the bioremediation of DBP in the environment.

Studies of Thermodynamic Properties and Relative Stability of Polybrominated Xanthones by Density Functional Theory

The thermodynamic properties of xanthone（XTH） and 135 polybrominated xanthones（PBXTHs） in the standard state have been calculated at the B3LYP/6-31G＊ level using Gaussian 03 program.The isodesmic reactions were designed to calculate the standard enthalpy of formation（△fHθ） and standard free energy of formation（△fGθ） of PBXTH congeners.The relations of these thermodynamic parameters with the number and position of Br atom substitution（NPBS） were discussed,and it was found that there exist high correlation between thermodynamic parameters（entropy（Sθ）,△fHθ and △fGθ） and NPBS.According to the relative magnitude of their △fGθ,the relative stability order of PBXTH congeners was theoretically proposed.The relative rate constants of formation reactions of PBXTH congeners were calculated,Moreover,the values of molar heat capacity at constant pressure（Cp,m） from 200 to 1000 K for PBXTH congeners were also calculated,and the temperature dependence relation of them was obtained,suggesting very good relationships between Cp,m and temperature（T,T^1 and T^2） for almost all PBXTH congeners.

Thermodynamic Properties and Relative Stability of Polyhydroxylated Dibenzo-p-dioxins Calculated by Density Functional Theory

In this work, partial thermodynamic properties of polyhydroxylated dibenzo-p-dioxins （PHODDs） are calculated by density functional theory （DFT） with the Gaussian 03 program at the B3LYP/6-311G^＊＊ level. By comparing the total energy Eθ values, it is found that two types of hydrogen bonds exist in PHODDs, one between a hydroxyl and the parent compound （dibenzop-dioxin） with bond energy of approximate 15.7 kJ/mol and the other between two ortho hydroxyl groups with higher bond energy of about 18.3 kJ/mol. Hydrogen bonds have an effect on the conformation stability. On the basis of evaluating the strength of these two types of hydrogen bonds, 75 most stable congeners are ascertained. The relations of calculated thermodynamic parameters （total energy E^θ, zero-point vibrational energy ZPE, correction value of thermal energy Ethθ, heat capacity at constant volume CV^θ） with the number and position of hydroxyl substitution （NPHOS） are also discussed. The results show that the NPHOS models can be used to predict the thermodynamic properties for PHODD congeners. In addition, the values of molar heat capacities at constant pressure （Cp,m） from 200 to 1000 K for PHODD congeners are calculated, and the temperature dependence relation of Cp,m is obtained with the least-squares method.

2D-QSAR Using MLR and 3D-QSAR Using CoMSIA Studies on the Toxicity of Aromatic Hydrocarbons on Larval Sinonvaculina Constricta

Aromatic hydrocarbons,one of the persistent organic pollutants（POPs）,has been usually found in mussels,accumulated for their hard mobility and activities in harbours and estuaries.In this study,based on the 96 hr-LC50 of 12 aromatic hydrocarbons with larval sinonvaculina constricta,three-dimensional quantitative structure-activity relationship（3D-QSAR） technique：comparative molecular similarity indices analysis（CoMSIA） and 2D-QSAR technique：multiple linear regression（MLR） were described to obtain more detailed insight into the structure-activity relationships between the molecular structure and bio-activity.The results show the MLR model based on density functional theory（DFT） calculation carried out at the B3LYP/6-311＊＊ level with Gaussian 03 program yielded a very good correlation with a coefficient squared R2 of 0.716 and a cross-validated Q2 of 0.874.The dipole moment and enthalpy,as the thermodynamic parameters,were two important factors influencing pLC50.Correspondingly,CoMSIA based on the partial least-squares（PLS） methodology with steric,electrostatic,hydrophobic,H-bond donor and acceptor fields contributing simultaneously were employed and the values of R2 and the cross validation with leave-One-Out（LOO） Q2LOO were 0.585 and 0.990,respectively,which reveals the structure features,such as the electronegative substituent（nitro-group）,hydrophobic groups（the benzene ring） and H-bond（nitro-group）,related to the toxicity.The results of 2D-QSAR employing MLR model and 3D-QSAR employing CoMSIA model provide the useful information for predicting the toxicity of other aromatic hydrocarbons by comparing the molecular structures of similar compounds.

Degradation of chlorothalonil by ultrasonic irradiation:Kinetics and impact factors

Factors on degradation of chlorothalonil(CLT) in water by high frequency ultrasonic irradiation were investigated.The effects of initial concentration of chlorothalonil,dosages of tertiary butyl alcohol,humic acid and initial pH value on degradation of chlorothalonil,as well as the reaction mechanism were studied.The results reveal that chlorothalonil could be effectively degradated by ultrasonic irradiation.The reaction constant value kapp decreased from 0.014 1 to 0.010 2 min-1 with the initial concentration increasing from 50 to 400 μg/L during 180 min irradiation.Tertiary butyl alcohol had negative effect on chlorothalonil degradation,while lower concentration of humic acid promoted the sonolysis,and kapp declined with the further concentration increasing.The kapp varied little when the pH value ranged from 3.10 to 10.28.It may be concluded that mechanical and pyrolysis process played main roles on the degradation of chlorothalonil in ultrasonic irradiation rather than ·OH attack.The electrical energy per order(EEo) values for sonolysis degradation of CLT were also calculated to evaluate the cost of the process.

Preparation of New Poly Silicate Iron Coagulants and Their Coagulation Property on Micro-polluted Water

The sodium silicate, ferric chloride, ferrous sulfate, sodium chlorate and other common inorganic materials were used to synthesize two new poly silicate iron coagulants： Polysilicate Ferric Chloride （PFSiC） and Polymeric Ferric Silicate Sulfate （PFSiS）. Their coagulation effect on micro-polluted water was compared with the poly ferric choride （PFC） saled in the market. The results showed that turbidity, organic matter, total phosphorus, total nitrogen removal rate ofPFSiC, PFSiS coagulant were better than PFC on micro-polluted water treatment at the same dosage. The coagulation effect of PFSiC was the best. The surface morphology of three coagulants was observed by scanning electron microscopy （SEM）, and the coagulation mechanism was discussed preliminarily.

Application of ensemble H-infinity filter in aquifer characterization andcomparison to ensemble Kalman filter

Though the ensemble Kalman filter （EnKF） has been successfully applied in many areas, it requires explicit and accurate model and measurement error information, leading to difficulties in practice when only limited information on error mechanisms of observational in-struments for subsurface systems is accessible. To handle the uncertain errors, we applied a robust data assimilation algorithm, the ensemble H-infinity filter （EnHF）, to estimation of aquifer hydraulic heads and conductivities in a flow model with uncertain/correlated observational errors. The impacts of spatial and temporal correlations in measurements were analyzed, and the performance of EnHF was compared with that of the EnKF. The results show that both EnHF and EnKF are able to estimate hydraulic conductivities properly when observations are free of error; EnHF can provide robust estimates of hydraulic conductivities even when no observational error information is provided. In contrast, the estimates of EnKF seem noticeably undermined because of correlated errors and inaccurate error statistics, and filter divergence was observed. It is concluded that EnHF is an efficient assimilation algorithm when observational errors are unknown or error statistics are inaccurate.

EQUILIBRIUM AND KINETIC ADSORPTION OF A REACTIVE BLACK KNB DYE ON POLYDIVINYLBENZENE AND STYRENE-DIVINYLBENZENE COPOLYMER RESINS

In this study, two polymeric resins with different pore sizes were synthesized to study comparative adsorption of reactive black KNB dye. Styrene-divinylbenzene copolymer resin NG-8 has an average pore size of 3.82 nm, about half of that of polydivinylbenzene resin NG-7 （6.90 nm）. NG-8 also has a surface acidity about 4 times that of NG-7, resulting in a much more negative surface of the former resin as compared to the latter at pH 6.05. Equilibrium adsorption of KNB was significantly influenced by the surface functionality of the resins, as evidenced by the observations that NG-8 adsorbed constantly less KNB than NG-7 and that the presence of CaCl2 enhanced the adsorption by both resins. The intra-particle diffusion appears to be the primary rate-limiting process. While the pores of both resins are accessible to KNB, the slower adsorption by NG-8 than by NG-7 suggests that the smaller pores of NG-8 further retard the intra-particle diffusion of KNB.

Studies of Structural and Thermodynamic Properties for Polychlorinated Thianthrenes by Density Functional Theory

The structural and thermodynamic （PCTAs） in the ideal gas state at 298.15 K and 1.013 properties of 75 polychlorinated thianthrenes ×10^5 Pa have been calculated at the B3LYP/6- 31G＊ level using Gaussian 98 program. Based on the output data of Gaussian, the isodesmic reactions were designed to calculate standard enthalpy of formation （△fH^θ） and standard free energy of formation （△fH^θ） of PCTAs congeners. The relations of these thermodynamic parameters with the number and position of C1 atom substitution （Npcs） were discussed, and it was found that there exists high correlation between thermodynamic parameters （total energy （TE）, zero-point vibrational energy （ZPE）, thermal correction to energy （Eth）, heat capacity at constant volume （Cv^θ）, entropy （S^θ）, enthalpy （H^θ）, free energy （G^θ）, standard enthalpies of formation （△fH^θ） and standard Gibbs energies of formation （△fG^θ）） and Npcs. On the basis of the relative magnitude of their △fG^θ, the order of relative stability of PCTA congeners was theoretically proposed. In addition, the correlations between structural parameters and Npcs were also discussed. The good correlations were found between molecular average polarizability （α）, energy of the highest occupied molecular orbital （EHOMO）, molecular volume （Vm） and Npcs, and all R^2 values are larger than 0.95. Moreover, it was supposed that the isomer groups with higher toxicity should be Tri-CTA and TCTA.

QSPR Study on the Boiling Points of Some Oxygenand Sulfur-containing Organic Compounds

Structural and thermodynamic parameters of 56 oxygen-containing and 56 sulfur- containing organic compounds were computed at the B3LPY/6-311G＊＊ level using density functional theory （DFT） method. Furthermore,the dependent equations between the experimental data of boiling points （Tb） and theoretical parameters were proposed with SPSS12.0 for windows software,whose correlation coefficients R2 are 0.933 and 0.945. These dependent equations were validated by cross-validation method （q2 are 0.923 and 0.929,respectively）. VIF （variance inflation factors） and t-value methods were also used to verify the significance and self-correlationship of each variable. Results indicate that our dependent equation exhibits good prediction ability,and molecular polarizability （α） is the main factor affecting the Tb of oxygen- and sulfur-containing organic compounds. To our interest,obvious dependence could also be found among the oxygen- and sulfur-containing organic compounds＇ experimental data of boiling points （Tb） with R^2 of 0.857.