Hydration and leaching characteristics of cement pastes made from electroplating sludge

The purpose of this study was to investigate the hydration and leaching characteristics of the pastes of belite-rich cements made from electroplating sludge. The compressive strength of the pastes cured for 1, 3, 7, 28, and 90 days was determined, and the condensation of silicate anions in hydrates was examined with the ²⁹Si nuclear magnetic resonance (NMR) technology. The leachabilities of the electroplating sludge and the hardened pastes were studied with the multiple toxicity characteristic leaching procedure (MTCLP) and the tank leaching test (NEN 7345), respectively. The results showed that the electroplating sludge continued to leach heavy metals, including nickel, copper, and zinc, and posed a serious threat to the environment. The belite-rich cement made from the electroplating sludge was abundant in hydraulic β-dicalcium silicate, and it performed well with regard to compressive-strength development when properly blended with ordinary Portland cements. The blended cement containing up to 40% the belite-rich cement can still satisfy the compressive-strength requirements of ASTM standards, and the pastes cured for 90 days had comparable compressive strength to an ordinary Portland cement paste. It was also found that the later hydration reaction of the blended cements was relatively more active, and high fractions of belite-rich cement increased the chain length of silicate hydrates. In addition, by converting the sludge into belite-rich cements, the heavy metals became stable in the hardened cement pastes. This study thus indicates a viable alternative approach to dealing with heavy metal bearing wastes, and the resulting products show good compressive strength and heavy-metal stability.     

Predicting Debris Yield From Burned Watersheds: Comparison of Statistical and Artificial Neural Network Models1

Abstract: Alluvial fans in southern California are continuously being developed for residential, industrial, commercial, and agricultural purposes. Development and alteration of alluvial fans often require consideration of mud and debris flows from burned mountain watersheds. Accurate prediction of sediment (hyper‐concentrated sediment or debris) yield is essential for the design, operation, and maintenance of debris basins to safeguard properly the general population. This paper presents results based on a statistical model and Artificial Neural Network (ANN) models. The models predict sediment yield caused by storms following wildfire events in burned mountainous watersheds. Both sediment yield prediction models have been developed for use in relatively small watersheds (50‐800 ha) in the greater Los Angeles area. The statistical model was developed using multiple regression analysis on sediment yield data collected from 1938 to 1983. Following the multiple regression analysis, a method for multi‐sequence sediment yield prediction under burned watershed conditions was developed. The statistical model was then calibrated based on 17 years of sediment yield, fire, and precipitation data collected between 1984 and 2000. The present study also evaluated ANN models created to predict the sediment yields. The training of the ANN models utilized single storm event data generated for the 17‐year period between 1984 and 2000 as the training input data. Training patterns and neural network architectures were varied to further study the ANN performance. Results from these models were compared with the available field data obtained from several debris basins within Los Angeles County. Both predictive models were then applied for hind‐casting the sediment prediction of several post 2000 events. Both the statistical and ANN models yield remarkably consistent results when compared with the measured field data. The results show that these models are very useful tools for predicting sediment yield sequences. The results can be used for scheduling cleanout operation of debris basins. It can be of great help in the planning of emergency response for burned areas to minimize the damage to properties and lives.     

Highly siliceous MCM-48 from rice husk ash for CO2 adsorption

Mesoporous MCM-48 silica was synthesized using a cationic-neutral surfactant mixture as the structure-directing template and rice husk ash (RHA) as the silica source. The MCM-48 samples were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N₂ physisorption and SEM. X-ray diffraction pattern of the resulting MCM-48 revealed typical pattern of cubic Ia3d mesophase. BET results showed the MCM-48 to have a surface area of 1024 m²/g and FT-IR revealed a silanol functional group at about 3460 cm⁻¹. Breakthrough experiments in the presence of MCM-48 were also carried out to test the material's CO₂ adsorption capacity. The breakthrough time for CO₂ was found to decrease as the temperature increased from 298 K to 348 K. The steep slopes observed shows the CO₂ adsorption occurred very quickly, with only a minimal mass transfer effect and very fast kinetics. In addition, amine grafted MCM-48, APTS-MCM-48 (RHA), was prepared with the 3-aminopropyltriethoxysilane (APTS) to investigate the effect of amine functional group in CO₂ separation. An order of magnitude higher CO₂ adsorption capacity was obtained in the presence of APTS-MCM-48 (RHA) compared to that with MCM-48 (RHA). These results suggest that MCM-48 synthesized from rice husk ash could be usefully applied for CO₂ removal.     

Deposition velocity of PM2.5 sulfate in the summer above a deciduous forest in central Japan

In order to increase knowledge of aerosol dry deposition for the regional assessment of acid deposition and transboundary air pollution in East Asia, an experimental study on PM2.5 sulfate deposition was implemented in the early summer of 2009. The experimental field was located in a deciduous forest at the foot of Mt. Asama, central Japan. Aerosol fluxes were obtained using the aerodynamic gradient method. Three aerosol samplers were placed on an experimental tower at 21, 24 and 27 m above the ground surface, and collected PM2.5 on filters for chemical analysis. Vertical concentration differences between 21 m and 27 m of PM2.5 sulfate were detected significantly when the concentration exceeded 1 μg m^?3. Mean deposition velocity was estimated to be 0.9 ± 1.0 cm s^?1 in the daytime and 0.3 ± 0.3 cm s^?1 in the nighttime. In the case that a height-dependent correction in the roughness sub-layer was taken into account, the deposition velocities increased more, especially in daytime. Higher deposition velocities in the daytime were associated with larger friction velocities and unstable conditions. The deposition velocities observed in this study were in agreement with other experimental results found in the literature. On the other hand, they were higher than those calculated by theoretical models. Two empirical parameterizations (Wesely, M.L., Cook, D.R., Hart, R.L., 1985. Measurement and parameterization of particulate sulfur dry deposition over grass. Journal of Geophysical Research 90, 2131–2143; Ruijgrok, W., Tieben, H., Eisinga, P., 1997. The dry deposition of particles to a forest canopy: a comparison of model and experimental results. Atmospheric Environment 31, 399–415) were validated by the observations. The general trend of higher daytime and lower nighttime deposition velocities was similar among the observation and the two parameterizations. The large variability found in the measurement was not reproduced by the parameterizations, because it is attributable to random error from the differences between the samplers. The observations were in accordance with the parameterization of Ruijgrok et al. (1997) for a forest, although much larger than that of Wesely et al. (1985) for grasslands. This indicates the large difference in aerosol deposition velocities between forests and grasslands.     

PCDDs, PCDFs, dioxin-like PCBs and indicator PCBs in soil from five selected areas in Slovakia

There is a lack of information regarding persistent organic pollutants (POPs) in soil from Slovakia. This paper reports the concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), 12 dioxin-like polychlorinated biphenyls (dl-PCBs) and 6 indicator PCBs associated with 32 soil samples collected in 2007 from areas in the vicinity up to several kilometres from four selected industrial PCDD/F sources in Slovakia and one background area.The results show that the total WHO₁₉₉₈-PCDD/F/dl-PCB-TEQ concentrations varied from 0.34 to 18.05 pg g⁻¹ dry weight (dw) and the average total TEQ concentrations in samples collected at the Šala, Košice, Krompachy and Dubová areas were 3.18, 2.64, 7.80, and 3.19 pg g⁻¹ dw respectively. The average of the total WHO₁₉₉₈-TEQ values in three soil samples representing the background Starina area was 0.66 pg g⁻¹ dw. The predominant contaminants among 2,3,7,8-substituted PCDD/Fs, dl-PCB, and indicator PCBs was OCDD, PCB 118, and PCB 153 respectively. The major contributors to the TEQ were 2,3,4,7,8-PeCDF, PCB 126, 1,2,3,7,8-PeCDD, PCB 156 and 1,2,3,4,7,8-HxCDF + 1,2,3,4,7,9-HxCDF in descending order.     

Study on photocatalytic degradation of gaseous dichloromethane using pure and iron ion-doped TiO2 prepared by the sol-gel method

The synthesis of TiO₂ and Fe–TiO₂ by sol–gel method is demonstrated and characterized. The characterization of TiO₂ and Fe–TiO₂ is performed with instruments, including TGA/DTA, FTIR, UV–Vis, N₂ adsorption and SEM. Dichloromethane is used for the photocatalytic activity test. From the results of dichloromethane photocatalyitc degradation, the calcined temperature of TiO₂ and the presence of water vapor influence the photocatalytic activity. The optimum doping amount of iron ions is 0.005 mol%, and this can enhance the photocatalytic activity, while too great an amount will make the iron ions become recombination centers for the electron–hole pairs and reduce the photocatalytic activity. UV–Vis diffuse reflectance spectra of Fe–TiO₂ show an increase in absorbency in the visible light region with the increase in iron ions doping concentration The intermediate of dichloromethane photodegradation includes CHCl₃, CCl₄, CH₂Cl₂ and COCl₂. The presence of iron ions may reduce the adsorption of Cl element on the surface of the photocatalyst.     

Characterization of a simple bacterial consortium for effective treatment of wastewaters with reactive dyes and Cr(VI)

A microbial consortia consisting of three bacteria isolated from tanning and textile wastewaters revealed high capacity to simultaneously bioaccumulate dye and Cr(VI). The identity of the bacteria were determined by 16S rRNA gene analysis to be closely related to Ochrobactrium sp., Salmonella enterica and Pseudomonas aeruginosa. Dependence of initial pH values and range of concentrations of the dye Reactive Black B (33.2-103.1 mg l(-1)) and Cr(VI) (19.9-127.6 mg l(-1)) were examined to find the effect of pH on the dye and Cr(VI) bioaccumulation. Optimal pH for growth of the consortia in media containing 35 mg l(-1) dye and 50 mg l(-1) Cr(VI) was determined to be around 8. The Cr(VI) bioaccumulation by the consortia was rapid in media containing molasses with or without reactive dye with a maximum Cr(VI) bioaccumulation yield ranging from 90% to 99% within a 2-4d period. A slightly lower yield for the dye bioaccumulation was measured with a maximum dye bioaccumulation of 80% at 59.3 mg l(-1) dye and 69.8 mg l(-1) Cr(VI). The highest specific Cr uptake value was obtained as 76.7 mg g(-1) at 117.1 mg l(-1) Cr(VI) and 50.8 mg l(-1) dye concentration. This ability to bioaccumulate dye and Cr(VI) was more efficient than the enriched sludge from which they were isolated.     

A model for prediction of product distributions for the reactions of phenol derivatives with hydroxyl radicals

In this study, with the intention of estimating the photocatalytic or photodegradation rates and finding certain predictors to be used for the determination of the most probable reaction path and the primary intermediate, the reactions of (*)OH radicals with 11 phenol derivatives including benzene were modeled. For 43 possible reaction routes, calculations of the geometric parameters, the electronic and thermodynamic properties of the reactants, the product radicals and the transition state complexes were performed with the semiempirical PM3 and DFT/B3LYP/6-31G(*) methods. The solvation effects were computed using COSMO as the solvation model. Based on the results of quantum mechanical calculations, the rate constants, the branching ratios and the product distributions of all the possible reaction paths were calculated by means of the transition state theory. Three predictors were determined for the prediction of the most probable transition state and the reaction path. The differences in the reaction rates were explained in terms of the presence of hydrogen bonds in the transition state complexes and the entropy effects. Finally the results obtained were compared with the available experimental data in order to assess the reliability of the proposed model.     

An 'artificial mussel' for monitoring heavy metals in marine environments

A new chemical sampling device, artificial mussel (AM), has been developed for monitoring metals in marine environments. This device consists of a polymer ligand suspended in artificial seawater within a Perspex tubing, and enclosed with semi-permeable gel at both ends. Laboratory and field experiments were carried out to examine the uptake of five metals (Cd, Cr, Cu, Pb and Zn) by the AM. Uptake of metals by AM was proportional to the exposure metal concentrations, and the AM was able to accumulate the ASV labile fractions of metals. Uptake and release of the metals of AM are similar to those of the mussel Perna viridis, but less affected by salinity and temperature. Field studies demonstrated that the AM can not only provide a time-integrated estimate of metals concentrations, but also allows comparisons of metal levels in different environments and geographical areas beyond the natural distribution limits of biomonitors.     

Assessment of heavy metals (Cd, Cr and Pb) in water, sediment and seaweed (Ulva lactuca) in the Pulicat Lake, South East India

The concentrations of three heavy metals chromium (Cr), cadmium (Cd) and lead (Pb) were examined in water, sediment and green algae (Ulva lactuca); collected from six different stations at Pulicat Lake, which receives effluents from industries located in North Chennai Coastal region. Concentrations of Cd (64.21 microg g(-1)) and Cr (28.51 microg g(-1)) were found to be high in sediment, whereas in green algae concentration of Pb (8.32 microg g(-1)) was higher than water and sediment samples. The relative abundance of these heavy metals in U. lactuca and sediment were found to be in the order Cd>Cr>Pb, whereas in water the ratio was found to be Cr>Pb>Cd. The seasonal variations in Cd and Pb followed a similar pattern in both seaweeds and sediments, but not in water samples. Spearman correlation coefficient study showed no significant correlation in the concentration of metals in U. lactuca, water and sediment samples.