Say Kee Ong

Factors affecting EDTA extraction of lead from lead-contaminated soils.

The effects of solution:soil ratio, major cations present in soils, and the ethylenediaminetetraacetic acid (EDTA):lead stoichiometric ratio on the extraction of lead using EDTA were studied for three different Superfund site soils, one rifle range soil, and one artificially lead-contaminated soil. Extraction of lead from the lead-contaminated soils was not affected by a solution:soil ratio as low as 3:1 but instead was dependent on the quantity of EDTA present. Results of the experiments showed that the extraction efficiencies were different for each soil. If sufficiently large amount of EDTA was applied (EDTA-Pb stoichiometric ratio greater than 10), most of the lead were extracted for all soils tested except for a Superfund site soil from a lead mining area. The differences in extraction efficiencies may be due to the major cations present in soils which may compete with lead for active sites on EDTA. For example, iron ions most probably competed strongly with lead for EDTA ligand sites for pH less than 6. In addition, copper and zinc may potentially compete with lead for EDTA ligand sites. Experimental results showed that addition of EDTA to the soil resulted in a very large increase in metals solubility. The total molar concentrations of major cations extracted were as much as 20 times the added molar concentration of EDTA. For some of the soils tested, lead may have been occluded in the iron oxides present in the soil which may affect lead extraction. While major cations present in the soil may be one of the factors affecting lead extraction efficiency, the type of lead species present also play a role.

Use of solvents to enhance PAH biodegradation of coal tar-contaminated soils.

Bioremediation of coal tar-contaminated soils containing polycyclic aromatic hydrocarbons (PAHs) is highly challenging because of the low solubility and strong sorption properties of PAHs. Five coal tar-contaminated soils from former manufactured gas plant (MGP) sites were pretreated with two solvents, acetone and ethanol to enhance the bioavailability of the PAH compounds. The biodegradation of various PAHs in the pretreated soils was assessed using soil slurry reactors. The total PAH degradation rates for soils pretreated with solvents were estimated to be about two times faster than soils that were not pretreated with solvents. For example, the total PAH first order degradation rate constants were 0.165+/-0.032, 0.147+/-0.020, and 0.076+/-0.009 day(-1) for Vandalia (EXC) soil that were pretreated with acetone, ethanol, and with no solvent, respectively. A distinctive advantage for soils pretreated with solvents was the enhanced removal of 5-ring PAH compounds such as benzo(a)pyrene and to a limited extent 4-ring compounds such as chrysene. Even for soils with 3.5% or more organic carbon content (two soils out of five), the degradation rate constants of chrysene were found to be two times faster than soils that were not pretreated. The degradation rate constants of benzo(a)pyrene were enhanced by 2-6 times for all five contaminated soils that were pretreated with solvents. To further elucidate trends that control the solvent treatment, the percent improvement in degradation rate constants (100 x rate constants for pretreated soils/rate constants for non-treated soils) for 16 PAHs were found to correlate well with the PAH partition coefficients (K(oc)). Except for phenanthrene and the clay fraction of the soil, correlations between the percent improvement in degradation rates constants and several physical properties of the soils were poor and sporadic. This implies that the enhancement in PAH availability using solvent treatment was driven by the distribution of the PAHs between the solvent and the adsorbed PAHs.

Contaminants of emerging environmental concern.

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Decomposition of nitrite under various pH and aeration conditions

Studies on the decomposition/oxidation of nitrite at differentpH values and aeration flow rates were investigated using abench-scale batch reactor. The conditions were pH 2.85, 3.50,5.80, 7.0, and 11.6, and with or without aeration at airflowrates of 1.50, 2.25, and 3.25 L min-1.Decomposition/oxidation of nitrite may be described by apseudo-first order expression, and the rate constants fornitrite decomposition/oxidation ranged from 1.2 ×10-6 s-1 to 1.12 × 10-4 s-1 depending on the experimental conditions. The rate ofdecomposition/oxidation of nitrite was found to increase for lowpH conditions and for high airflow rates. The experimentalresults showed that the dominant reaction in thedecomposition/oxidation of nitrite in low pH solutions and inthe presence of some aeration was most probably thedecomposition of nitrous acid to NO and NO2. Oxidation ofnitrite to nitrate appeared to proceed in a smaller proportionin comparison to the breakdown of nitrous acid to nitrogen oxidecompounds. Results from this study showed that emissions ofnitrogen oxides from nitrite-containing solutions are possible ifthe solutions were agitated and the pHs of the solutions wereless than 6.

Impact of solids residence time on biological nutrient removal performance of membrane bioreactor.

Impact of long solids residence times (SRTs) on nutrient removal was investigated using a submerged plate-frame membrane bioreactor with anaerobic and anoxic tanks. The system was operated at 10, 25, 50 and 75 days SRTs with hydraulic retention times (HRTs) of 2 h each for the anaerobic and anoxic tanks and 8 h for the oxic tank. Recirculation of oxic tank mixed liquor into the anaerobic tank and permeate into the anoxic tank were fixed at 100% each of the influent flow. For all SRTs, percent removals of soluble chemical oxygen demand were more than 93% and nitrification was more than 98.5% but total nitrogen percent removal seemed to peak at 81% at 50 days SRT while total phosphorus (TP) percent removal showed a deterioration from approximately 80% at 50 days SRT to 60% at 75 days SRT. Before calibrating the Biowin((R)) model to the experimental data, a sensitivity analysis of the model was conducted which indicated that heterotrophic anoxic yield, anaerobic hydrolysis factors of heterotrophs, heterotrophic hydrolysis, oxic endogenous decay rate for heterotrophs and oxic endogenous decay rate of PAOs had the most impact on predicted effluent TP concentration. The final values of kinetic parameters obtained in the calibration seemed to imply that nitrogen and phosphorus removal increased with SRT due to an increase in anoxic and anaerobic hydrolysis factors up to 50 days SRT but beyond that removal of phosphorus deteriorated due to high oxic endogenous decay rates. This indirectly imply that the decrease in phosphorus removal at 75 days SRT may be due to an increase in lysis of microbial cells at high SRTs along with the low food/microorganisms ratio as a result of high suspended solids in the oxic tank. Several polynomial correlations relating the various calibrated kinetic parameters with SRTs were derived. The Biowin((R)) model and the kinetic parameters predicted by the polynomial correlations were verified and found to predict well the effluent water quality of the MBR at 35 days SRT.

Air sparging effectiveness: laboratory characterization of air-channel mass transfer zone for VOC volatilization

Air sparging in conjunction with soil vapor extraction is one of many technologies currently being applied for the remediation of groundwater contaminated with volatile organic compounds (VOCs). Mass transfer at the air-water interface during air sparging is affected by various soil and VOC properties. In this study with a single air-channel apparatus, mass transfer of VOCs was shown to occur within a thin layer of saturated porous media next to the air channel. In this zone, the VOCs were found to rapidly deplete during air sparging resulting in a steep concentration gradient while the VOC concentration outside the zone remained fairly constant. The sizes of the mass transfer zone were found to range from 17 to 41 mm or 70d(50) and 215d(50) (d(50)=mean particle size) for low organic carbon content media (<0.01% OC). The size of the mass transfer zone was found to be proportional to the square root of the aqueous diffusivity of the VOC, and was affected by the mean particle size, and the uniformity coefficient. Effects of the volatility of the VOCs as represented by the Henrys law constants and the airflow rates on the mass transfer zone were found to be negligible but VOC mass transfer from air-water interface to bulk air phase seems to play a role. A general correlation for predicting the size of the mass transfer zone was developed. The model was developed using data from nine different VOCs and verified by two other VOCs. The existence of the mass transfer zone provides an explanation for the tailing effect of the air phase concentration under prolonged air sparging and the rebound in the VOC air phase concentration after the sparging system is turned off.

Effect of pH on transport of Pb2+, Mn2+, Zn2+ and Ni2+ through lateritic soil: Column experiments and transport modeling

This study investigated the effects of pH on the transport of Pb2+, Mn2+, Zn2+ and Ni2+ through lateritic soil columns. Model results by fitting the symmetric breakthrough curves (BTCs) of bromide (Br-) with CXTFIT model suggested that physical non-equilibrium processes were absent in the columns. The heavy metal BTCs were, however, asymmetrical and exhibited a tailing phenomenon, indicating the presence of chemical non-equilibrium processes in the columns. The retardation factors of Pb2+ were the largest of the four metal ions at both pH 4.0 (33.3) and pH 5.0 (35.4). The use of Langmuir isotherm parameters from batch studies with HYDRUS-1D did not predict the BTCs well. Rather the two-site model (TSM) described the heavy metal BTCs better than the equilibrium linear/nonlinear Langmuir model. The fraction of instantaneous sorption sites (f) of all four metal ions on the lateritic soil was consistently about 30%-44% of the total sorption sites.

Air sparging: Air‐water mass transfer coefficients

Experiments investigating the mass transfer of several dissolved volatile organic compounds (VOCs) across the air-water interface were conducted using a single-air- channel air-sparging system. Three different porous media were used in the study. Air velocities ranged from 0.2 cm s−1 to 2.5 cm s−1. The tortuosity factor for each porous medium and the air-water mass transfer coefficients were estimated by fitting experimental data to a one-dimensional diffusion model. The estimated mass transfer coefficients KG ranged from 1.79 × 10−3 cm min−1 to 3.85 × 10−2 cm min−1. The estimated lumped gas phase mass transfer coefficients KGa were found to be directly related to the air diffusivity of the VOC, air velocity, and particle size, and inversely related to the Henrys law constant of the VOCs. Of the four parameters investigated, the parameter that controlled or had a dominant effect on the lumped gas phase mass transfer coefficient was the air diffusivity of the VOC. Two empirical models were developed by correlating the Damkohler and the modified air phase Sherwood numbers with the air phase Peclet number, Henrys law constant, and the reduced mean particle size of porous media. The correlation developed in this study may be used to obtain better predictions of mass transfer fluxes for field conditions.

Modeling of air sparging of VOC-contaminated soil columns

Abstract Air sparging is a remediation technology currently being applied for the restoration of sites contaminated with volatile organic compounds (VOCs). Attempts have been made by various researchers to model the fate of VOCs in the gas and liquid phase during air sparging. In this study, a radial diffusion model with an air–water mass transfer boundary condition was developed and applied for the prediction of VOC volatilization from air sparging of contaminated soil columns. The approach taken was to use various parameters such as mass transfer coefficients and tortuosity factors determined previously in separate experiments using a single air channel apparatus and applying these parameters to a complex system with many air channels. Incorporated in the model, is the concept of mass transfer zone (MTZ) where diffusion of VOCs in this zone was impacted by the volatilization of VOCs at the air–water interface but with negligible impact outside the zone. The model predicted fairly well the change in the VOC concentrations in the exhaust air, the final average aqueous VOC concentration, and the total mass removed. The predicted mass removal was within 1% to 20% of the actual experimental mass removed. The results of the model seemed to suggest that air-sparged soil columns may be modeled as a composite of individual air channels surrounded by a MTZ. For a given air flow rate and air saturation, the VOC removal was found to be inversely proportional to the radius of the air channel. The approach taken provided conceptual insights on mass transfer processes during air sparging operations.

Competitive sorption and transport of Pb2+, Ni2+, Mn2+, and Zn2+ in lateritic soil columns.

Knowledge of sorption and transport of heavy metals in soils in the presence of other metals is crucial for assessing the environmental risk of these metals. Competitive sorption and transport of four metals, Pb(2+), Ni(2+), Zn(2+), and Mn(2+), were investigated using multi-metal column experiments with lateritic soils obtained from a gold mine impacted by acid mine drainage. Based on Pb(2+) breakthrough time for single-metal system at a pH of approximately 5, the sorption capacity of Pb(2+) was estimated to be higher in lateritic soil than the other metals. For multi-metal systems, the estimated retardation factors for the metals from highest to lowest were: Pb(2+)>Zn(2+)∼ Ni(2+)>Mn(2+), suggesting the mobility of metals through lateritic soil for a multi-metal system would be in the order of Mn(2+)>Ni(2+)∼ Zn(2+)>Pb(2+). For binary and multi-metal systems, the estimated sorption capacities of individual metals were found to be lower than the sorption capacities in single metal system - indicating possible competition for sorption sites. Mass recoveries estimates showed that the sorption of metals was more reversible under competitive multi-metal systems than in single metal systems.