Mechanisms of Competitive Adsorption Between Trace Organic Contaminants and Natural Organic Matter on Activated Carbon

Mechanisms of Competitive Adsorption Between Trace Organic Contaminants and Natural Organic Matter on Activated Carbon
Author: Li Ding
Publisher:
Total Pages:
Release: 2010
Genre:
ISBN:

Activated carbon adsorption is widely used in water treatment for removal of various organic micropollutants; nonetheless, the presence of natural organic matter (NOM) in source water can reduce its efficiency for micropollutant removal. NOM has been shown to compete with target contaminant via different mechanisms: direct competition for available adsorption sites which reduces equilibrium capacity for target compounds, blocking of pore entrance which reduces diffusion rate of the target compounds, and covering of surface sites which may actually enhances diffusion rate of the target compounds. The objective of this dissertation study was to further elucidate the individual competitive effects, to investigate how pore sizes of adsorbents and molecular structure of competing compounds affect competition and to gain a comprehensive understanding of the competitive adsorption. Atrazine, a widely used herbicide in the United States, was used as the trace-level target contaminant and NOM from different source waters as well as NOM surrogates were used as the competing compounds. Powdered activated carbons (PACs) with different pore size distribution (PSD) were used. The PSD was found to have great influence on the pore blockage (PB) effect caused by NOM. The equilibrium capacity of the NOM used in this study was best correlated to the amount of pores of diameter 15-50 ©5, which was also inversely related to the magnitude of the pore blockage effect. Activated carbon that has more surface area in this pore size range had a smaller PB effect on atrazine adsorption kinetics at the same NOM loading. This finding indicated that mesopores are important in realizing adsorption capacity for trace compounds by alleviating the adverse PB effect. The site covering effect was confirmed with additional types of PACs and various competing compounds. More important, the correlation equation that describes the enhanced surface diffusion coefficient for atrazine as a function of the loading of the site-covering compounds was found to be independent of either the PAC type or the competing compound type. The key component was to quantify the competing compound as the equivalent background compound (EBC), which reflected the extent of active sites being covered. iii The site competing effect, the site covering effect and the pore blocking effect were evaluated for five NOM surrogates with different sizes. The smaller molecules were generally more effective in reducing the equilibrium capacity of the target compound. However, for molecules of similar molecular weight, elongated molecules tended to have more equilibrium effect than round molecules. From a kinetic perspective, the enhancement in diffusivity was within one order of magnitude for all five surrogates, while the extent of the PB effect was greatly relying on molecular size that large-sized surrogates caused a much stronger PB effect. Therefore, the overall kinetic effect was dependent on molecular size and the PB effect was usually dominant except for very small molecules. Consistent with the enhanced kinetics associated with pre-adsorbed site-covering competing compounds, atrazine preloading was found to also increase the diffusion coefficient of atrazine, and the extent of enhancement caused by atrazine was greater than that caused by competing compounds. Several explanations were proposed for the difference, which include the micropore filling hypothesis and the artifact associated with the EBC method that was used for site-covering loading quantification.

Effects of Activated Carbon Characteristics on Organic Contaminant Removal

Effects of Activated Carbon Characteristics on Organic Contaminant Removal
Author: Detlef R. U. Knappe
Publisher: IWA Publishing
Total Pages: 100
Release: 2004-01-01
Genre: Science
ISBN: 1843398419

Many water treatment plants need to remove objectionable trace organic compounds, and activated carbon adsorption is often the best available technology. Utilities face the challenge of having to choose from a large variety of activated carbons, and iodine number or BET surface area values are often utilized in the selection process. Although neither parameter correlates well with adsorption capacities, alternative activated carbon selection criteria based on fundamental adsorbent and adsorbate properties are lacking to date. The first objective of this research was to systematically evaluate the effects of activated carbon pore structure and surface chemistry on the adsorption of two common drinking water contaminants: the relatively polar fuel oxygenate methyl tertiary-butyl ether (MTBE) and the relatively nonpolar solvent trichloroethene (TCE). The second objective was to develop simple descriptors of activated carbon characteristics that facilitate the selection of suitable adsorbents for the removal of organic contaminants from drinking water.Originally published by AwwaRF for its subscribers in 2003 This publication can also be purchased and downloaded via Pay Per View on Water Intelligence Online - click on the Pay Per View icon below

Kinetics of Trace Metals Sorption on and Desorption from Soils

Kinetics of Trace Metals Sorption on and Desorption from Soils
Author: Zhenqing Shi
Publisher:
Total Pages:
Release: 2006
Genre: Chemical kinetics
ISBN: 9780542519369

Understanding the kinetics of trace metals sorption and desorption on soils is important for better prediction of metal behavior in the environment. In this dissertation, the effect of solution chemistry and soil composition on trace metal sorption and desorption kinetics was investigated. Based on the experimental results, predictive kinetics models were formulated and successfully used to describe the kinetics of trace metals sorption and desorption on a variety of soils. The kinetics experiments were conducted with a stirred-flow method. A number of soil samples, which cover a wide range of soil properties from USA and European countries, were selected to test the effect of soil composition. The effects of solution chemistry, pH, metal loadings, and dissolved organic matter (DOM) concentration, were also systematically examined. Most of kinetics experiments were run with two trace metals, copper and zinc, which demonstrated very different kinetics behaviors. The solution pH has significant effect on the Cu and Zn sorption and desorption kinetics which can be accounted by the proton competition. DOM greatly enhanced Cu release but had little effect on Zn, attributed to formation of strong Cu-DOM complex decreasing the Cu ion re-adsorption on soils. Among all soil components, soil organic matter (SOM) is the dominant phase controlling Cu and Zn sorption and desorption kinetics. The effect of residence time was also tested. The kinetics models were formulated and successfully used to describe the Cu and Zn sorption and desorption kinetics under different solution chemistry and soil compositions. The models are based on the mass balance of the flow system and incorporate the chemical reactions between metals and soils. For Zn, a two-site kinetics model, including one fast and one slow site, was necessary. The soil organic carbon (SOC) is the major model parameter accounting for the effect of soil properties on Zn sorption and desorption kinetics. The organic carbon normalized sorption rate coefficients can be applied to different soils based on their SOC concentrations. One set of rate coefficients can be applied to different influent Zn concentrations, which corresponds to the linear portion of the Zn sorption isotherm. The sorption rate coefficients were dependent on solution pH which was accounted for by Zn and proton competition. The same model parameters can be applied to different flow rates. (Abstract shortened by UMI.).

Effects of Activated Carbon Surface Chemistry and Pore Structure on the Adsorption of Trace Organic Contaminants from Aqueous Solution

Effects of Activated Carbon Surface Chemistry and Pore Structure on the Adsorption of Trace Organic Contaminants from Aqueous Solution
Author:
Publisher:
Total Pages:
Release: 2002
Genre:
ISBN:

The principal objectives of this research were (1) to identify activated pore structure and surface chemistry characteristics that assure the effective removal of trace organic contaminants from aqueous solution, and (2) to develop a procedure to predict the adsorption capacity of activated carbons from fundamental adsorbent and adsorbate properties. To systematically evaluate pore structure and surface chemistry effects on the adsorption of organic micropollutants from aqueous solution, a matrix of activated carbon fibers (ACFs) with three activation levels and four surface chemistry levels was prepared and characterized. In addition, three commercially available granular activated carbons (GACs) were studied to verify whether correlations developed for the ACF matrix are valid for adsorbents that are typically used for water treatment. BET surface area, pore size distribution, elemental composition, point of zero charge and infrared spectroscopy data were obtained to characterize the adsorbents. The results showed that the ACF matrix prepared in this study permits a fairly independent evaluation of surface chemistry and pore structure effects on organic contaminant adsorption from aqueous solution. Methyl tertiary-butyl ether (MTBE), a relatively hydrophilic adsorbate, and trichloroethene (TCE), a relatively hydrophobic adsorbate, served as adsorbate probes. To evaluate the effects of natural organic matter (NOM) on MTBE and TCE adsorption capacities, isotherm experiments were conducted in ultrapure water and Sacramento-San Joaquin Delta water. With respect to surface chemistry, both single-solute isotherms and isotherms in the presence of NOM indicated that hydrophobic adsorbents more effectively removed TCE and MTBE from aqueous solution than hydrophilic adsorbents. Enhanced water adsorption on polar surface sites explained the poorer performance of the hydrophilic adsorbents. Based on the elemental composition of the low-ash carbons evaluated in this study, act.