Removal of a synthetic organic chemical by PAC-UF systems--I: Theory and modeling

Based on the age distributions of powdered activated carbon (PAC) in reactors, the competitive bi-solute isotherm and the pore-surface diffusion mechanism, a model was developed to predict the removal of a trace synthetic organic chemical (SOC) when PAC was applied to an ultrafiltration (UF) membrane system. Independent experiments evaluated the input parameters for the model. The pore diffusion in liquid-filled pore was the dominant internal mass transfer mechanism in a PAC particle and the surface diffusion mechanism was neglected in the model. Model prediction was compared with data from pilot plant experiments treating simazine in natural water. Due to the blending and the increasing PAC in the UF loop, a transient behavior of effluent simazine concentration was observed in the UF effluent. The model predicted successfully this periodical variation of the simazine concentration in the UF loop effluent, as well as the simazine concentration in the effluent from the PAC slurry contactor. The faithful model prediction required the modeling of the phenomenon of adsorption/desorption of an SOC on membrane itself.     

MTBE adsorption on alternative adsorbents and packed bed adsorber performance

Widespread use of the fuel additive methyl tertiary-butyl ether (MTBE) has led to frequent MTBE detections in North American and European drinking water sources. The overall objective of this research was to evaluate the effectiveness of a silicalite zeolite, a carbonaceous resin, and a coconut-shell-based granular activated carbon (GAC) for the removal of MTBE from water. Isotherm and short bed adsorber tests were conducted in ultrapure water and river water to obtain parameters describing MTBE adsorption equilibria and kinetics and to quantify the effect of natural organic matter (NOM) on MTBE adsorption. Both the silicalite zeolite and the carbonaceous resin exhibited larger MTBE adsorption uptakes than the tested GAC. Surface diffusion coefficients describing intraparticle MTBE mass transfer rates were largest for the GAC and smallest for the carbonaceous resin. Pilot tests were conducted to verify MTBE breakthrough curve predictions obtained with the homogeneous surface diffusion model and to evaluate the effect of NOM preloading on packed bed adsorber performance. Results showed that GAC was the most cost-competitive adsorbent when considering adsorbent usage rate only; however, the useful life of an adsorber containing silicalite zeolite was predicted to be approximately 5-6 times longer than that of an equally sized adsorber containing GAC. Pilot column results also showed that NOM preloading did not impair the MTBE removal efficiency of the silicalite zeolite. Thus, it may be possible to regenerate spent silicalite with less energy-intensive methods than those required to regenerate GAC.     

Impact of pH on the adsorption and desorption kinetics of 2-nitrophenol on activated carbons

The adsorption and desorption kinetics of 2-nitrophenol (2NP) from aqueous solutions using F-400 and WV-B granular activated carbons (GAC) have been studied at pHs 1, 4.6 and 13, using batch tests. Adsorption and desorption kinetics of 2NP on to both carbons were adequately described by the homogeneous solid surface diffusion model (HSSD). The adsorption and desorption kinetics can be predicted at different pHs by using adsorption kinetics parameters of the pH 4.6 and the isotherm parameters for the corresponding pH. Thus, the differences in the rates of adsorption are primarily attributable to the differences in the equilibrium loadings at the various pHs.     

Pore blockage effect of NOM on atrazine adsorption kinetics of PAC: the roles of PAC pore size distribution and NOM molecular weight

Natural organic matter (NOM) in natural water has been found to have negative effects on the adsorption of various trace organic compounds by activated carbon through two major mechanisms: direct competition for sites and pore blockage. In this study, the pore blockage effect of NOM on atrazine adsorption kinetics was investigated. Two types of powdered activated carbon (PAC) and three natural waters were tested to determine the roles of PAC pore size distribution and NOM molecular weight distribution in the pore blockage mechanism. When PAC was preloaded with natural water, the pore blockage effect of the NOM was found to cause a reduction of up to more than two orders of magnitude in the surface diffusion rate of atrazine compared to simultaneous adsorption of atrazine and NOM with fresh PAC. The surface diffusion coefficient of atrazine for preloaded PAC decreased with a decrease in PAC dose or an increase in NOM surface concentration. Because of the pore blockage effect of NOM, a 30% drop in atrazine removal was observed in a continuous flow PAC/microfiltration (MF) system after 7 days of contact compared to the removal predicted from the batch isotherm test. Large micropores and mesopores were found to play an important role in alleviating the effect of pore blockage. A PAC with a relatively large fraction of large micropore and mesopores was shown to suffer much less from the pore blockage effect compared with a PAC that had a much smaller fraction of large pores. Natural waters with different NOM molecular weight distribution caused different extent of pore blockage. The NOM molecules with molecular weight between 200 and 700 Dalton appeared to be responsible for the pore blockage effect.     

Competitive adsorption of benzoic acid and p-nitrophenol onto activated carbon: isotherm and breakthrough curves

Three series of batch tests at 25 degrees C were performed to determine the benzoic acid and p-nitrophenol (PNP) binary adsorption isotherms onto GAC in the aqueous solutions and the experimental data were fitted to the extended Langmuir isotherm model successfully. The experimental data and the isotherm model parameters showed that the GAC used in this study had a higher affinity to PNP than benzoic acid. Three column tests were performed to determine the breakthrough curves and effluent solution pH with varying feed compositions. According to the experimental results, the weakly adsorbed BA exhibited an intermediate zone of effluent concentration higher than its feed one; the effluent solution pH could serve as a good indicator for breakthrough. The breakthrough curves with varying feed compositions could be predicted by the non-linear wave propagation theory satisfactorily. Only the adsorption isotherm models were required to construct the composition path diagram with which the breakthrough curves could be predicted.     

Application of a three-component competitive adsorption model to evaluate and optimize granular activated carbon systems

A recently developed kinetic model for granular activated carbon (GAC) adsorbers (COMPSORB-GAC) that quantitatively describes the adsorption of trace organic contaminant in the presence of competing natural organic matter (NOM) was applied to evaluate the performance of different GAC system configurations: conventional fixed-bed adsorbers, layered upflow carbon adsorbers (LUCA), and moving-bed adsorbers (with few or many bed sections). COMPSORB-GAC separately tracks the adsorption of three components: a trace compound, a strongly competing NOM fraction that reduces trace compound equilibrium capacity, and a pore-blocking NOM fraction that reduces kinetics. Performance was simulated for various design criteria and with model parameters derived for two natural waters with significantly different NOM concentrations. For the range of simulated conditions and with baseline performance defined by a fixed-bed adsorber, LUCA generally reduced carbon usage rates (CURs) by 15-35%. A 2-section and a 16-section moving-bed reactor reduced baseline CURs by 20-30% and 45-55%, respectively. Projected CURs for the water source with a relatively high NOM concentration were 2-3 times higher for all reactor configurations and indicated that NOM preloading would cause performance deterioration in deep GAC beds, which highlights the importance of source water quality. These results show how COMPSORB-GAC can be used in a comprehensive, site-specific optimization of GAC systems to ensure robust system performance and to balance capital and operating costs.     

The effects of dissolved natural organic matter on the adsorption of synthetic organic chemicals by activated carbons and carbon nanotubes

Understanding the influence of natural organic matter (NOM) on synthetic organic contaminant (SOC) adsorption by carbon nanotubes (CNTs) is important for assessing the environmental implications of accidental CNT release and spill to natural waters, and their potential use as adsorbents in engineered systems. In this study, adsorption of two SOCs by three single-walled carbon nanotubes (SWNTs), one multi-walled carbon nanotube (MWNT), a microporous activated carbon fiber (ACF) [i.e., ACF10] and a bimodal porous granular activated carbon (GAC) [i.e., HD4000] was compared in the presence and absence of NOM. The NOM effect was found to depend strongly on the pore size distribution of carbons. Minimal NOM effect occurred on the macroporous MWNT, whereas severe NOM effects were observed on the microporous HD4000 and ACF10. Although the single-solute adsorption capacities of the SWNTs were much lower than those of HD4000, in the presence of NOM the SWNTs exhibited adsorption capacities similar to those of HD4000. Therefore, if released into natural waters, SWNTs can behave like an activated carbon, and will be able to adsorb, carry, and transfer SOCs to other systems. However, from an engineering application perspective, CNTs did not exhibit a major advantage, in terms of adsorption capacities, over the GAC and ACF. The NOM effect was also found to depend on molecular properties of SOCs. NOM competition was more severe on the adsorption of 2-phenylphenol, a nonplanar and hydrophilic SOC, than phenanthrene, a planar and hydrophobic SOC, tested in this study. In terms of surface chemistry, both adsorption affinity to SOCs and NOM effect on SOC adsorption were enhanced with increasing hydrophobicity of the SWNTs.     

考虑非均衡吸附的多孔介质中循环注入污染物运移规律

由经典的吸附解吸作用下污染物运移控制方程出发,将Freundlich线性等温吸附模型中溶质浓度上升、下降过程视为吸附、解吸过程,从而建立了非均衡吸附问题理论模型;并给出了累计质量分数及相对浓度的相关表达。利用Comsol Multiphysics数值分析方法讨论了三角函数、高斯脉冲函数循环注入下污染物运移规律,结果表明:吸附、解吸平衡常数的差值对污染物吸附量有较大影响,其值越大吸附量则越大;随着弥散度的增大,穿透曲线峰值有先增大后减小趋势,且穿透过程越久。此外,对于连续注入,注入时间存在一个临界值,小于该值时溶质浓度峰值随注入时间的增大而增大,而大于该值时溶质浓度峰值恒等于注入浓度平均值;且注入时间越大峰值出现时刻越晚;而相对浓度随注入时间的增大而减小。     

Comparison of the removal of hydrophobic trace organic contaminants by forward osmosis and reverse osmosis

We compared the rejection behaviours of three hydrophobic trace organic contaminants, bisphenol A, triclosan and diclofenac, in forward osmosis (FO) and reverse osmosis (RO). Using erythritol, xylose and glucose as inert reference organic solutes and the membrane pore transport model, the mean effective pore size of a commercial cellulose-based FO membrane was estimated to be 0.74 nm. When NaCl was used as the draw solute, at the same water permeate flux of 5.4 L/m² h (or 1.5 μm/s), the adsorption of all three compounds to the membrane in the FO mode was consistently lower than that in the RO mode. Rejection of bisphenol A and diclofenac were higher in the FO mode compared to that in the RO mode. Because the molecular width of triclosan was larger than the estimated mean effective membrane pore size, triclosan was completely rejected by the membrane and negligent difference between the FO and RO modes could be observed. The difference in the separation behaviour of these hydrophobic trace organics in the FO (using NaCl the draw solute) and RO modes could be explained by the phenomenon of retarded forward diffusion of solutes. The reverse salt flux of NaCl hinders the pore diffusion and subsequent adsorption of the trace organic compounds within the membrane. The retarded forward diffusion effect was not observed when MgSO₄ and glucose were used as the draw solutes. The reverse flux of both MgSO₄ and glucose was negligible and thus both adsorption and rejection of BPA in the FO mode were identical to those in the RO mode.     

Effect of natural organic matter on powdered activated carbon adsorption of trace contaminants: characteristics and mechanism of competitive adsorption

Batch adsorption experiments using powdered activated carbon (PAC) to remove trace synthetic organic chemicals (SOCs) from water containing natural organic matter (NOM) were conducted. The percentage of SOC removed at any contact time and at any PAC dose was observed to be independent of the initial SOC concentration. Equations derived from the ideal adsorbed solution theory and the pore surface diffusion model validated this observation. For the strongly adsorbing SOCs (simazine and simetryn), the percentage of SOC removed was independent only at low initial SOC concentrations. The NOM fraction competing with the weakly adsorbing SOC (asulam) constituted a larger percentage of the total NOM than that competing with the strongly adsorbing SOCs. Although the adsorptive capacities of the SOCs were greatly reduced in water containing NOM compared with those in pure water, the change in the pore diffusion coefficient was insignificant. Therefore, NOM competed with the SOCs for adsorption sites, reducing the adsorptive capacity, but the amount of NOM loading was not so severe that it blocked or filled the pores, hindering the internal diffusion of the SOCs.     

考虑非线性吸附时污染物在半无限黏土中的一维扩散解

在考虑分段吸附等温模式的基础上,建立了污染物在黏土中的一维扩散模型。并得到了简化求解条件下的解析解。模型引入了移动边界以说明当污染物在黏土孔隙水中的浓度达到某一较高值后,阻滞因子将发生显著变化。通过该解分析了黏土颗粒对污染物的这种非线性吸附特征对其在黏土中扩散的影响。算例分析表明本文解得到的计算结果介于不考虑吸附情形和考虑线性吸附情形得到的结果之间。对于文中算例,考虑线性等温线得到的污染物击穿时间为按本文解得到的击穿时间的2.2倍。因此,在浓度较大时,采用线性吸附等温模线会得到偏不安全的结果。该解相对较简单,并可用于验证各种数值模型,拟合试验数据等。     

Discriminating and assessing adsorption and biodegradation removal mechanisms during granular activated carbon filtration of microcystin toxins

Microcystins are cyanobacterial toxins that are problematic for water authorities due to their resistance to conventional water treatment. Granular activated carbon (GAC) filtration has been shown to be effective in removing microcystin from water using both adsorption and biodegradation removal mechanisms; however, little is known regarding which removal mechanism predominates and to what extent. In this study, microcystin removal due to adsorption and biodegradation in GAC filtration were discriminated and assessed by commissioning three parallel laboratory columns, including a sterile GAC column, a conventional GAC column and a sand column. The results demonstrate that biodegradation is an efficient removal mechanism once it commences and that the rate of biodegradation was dependent upon temperature and initial bacterial concentration. Adsorption of microcystins was prevalent during the initial stages of the GAC columns and was modelled using the homogeneous surface diffusion model (HSDM). The HSDM provided evidence that an active biofilm present on the surface of the conventional GAC hindered adsorption of microcystin compared with the sterile GAC with no active biofilm. Up to 70% removal of microcystin-LR was still observed after 6 months of operation of the sterile GAC column, indicating that adsorption still played a vital role in the removal of this toxin.     

Removal of MIB and geosmin using granular activated carbon with and without MIEX pre-treatment

This study assessed the impact of MIEX pre-treatment, followed by either coagulation or microfiltration (MF), on the effectiveness of pilot granular activated carbon (GAC) filters for the removal of the taste and odour compounds, 2-methylisoborneol (MIB) and geosmin, from a surface drinking water source over a 2-year period. Complete removal of MIB and geosmin was achieved by all GAC filters for the first 10 months, suggesting that the available adsorption capacity was sufficient to compensate for differences in dissolved organic carbon (DOC) entering the GAC filters.Reduction of empty bed contact time (EBCT), in all but one GAC filter, resulted in breakthrough of spiked MIB and geosmin, with initial results inconclusive regarding the impact of MIEX pre-treatment. MIB and geosmin removal increased over the ensuing 12 months until complete removal of both MIB and geosmin was again achieved in all but one GAC filter, which had been pre-chlorinated. Autoclaving and washing the GAC filters had minimal impact on geosmin removal but reduced MIB removal by 30% in all but the pre-chlorinated filter, confirming that biodegradation impacted MIB removal. The impact of biodegradation was greater than any impact on GAC adsorption arising from DOC differences due to MIEX pre-treatment. It is not clear whether, at a lower initial EBCT, MIEX pre-treatment may have impacted on the adsorption capacity of the virgin GAC.The GAC filter maintained at the longer EBCT, which was also pre-chlorinated, completely removed MIB and geosmin for the period of the study, suggesting that the greater adsorption capacity was compensating for any decrease in biological degradation.     

Electrochemical regeneration of field spent GAC from two water treatment plants

The effectiveness of on-site thermal regeneration of field-spent granular activated carbon (GAC) from two municipal drinking water facilities was compared with bench-scale electrochemical regeneration, a novel regeneration technology. The regeneration method was evaluated using aqueous natural organic material (NOM) adsorption, iodine number analysis, and surface area analysis. In contrast to the large electrochemical regeneration efficiencies reported in the literature for GAC loaded with phenolics and other individual organic compounds, the electrochemical reactor tested was only able to regenerate 8-15% of the NOM adsorption capacity of the field spent GAC. In contrast, thermal reactivation achieved up to 103% regeneration efficiency. To more accurately assess the efficiency of regeneration processes for water treatment applications, GAC should be loaded in continuous-flow columns and not batch rectors. The iodine number analysis yielded higher efficiency values, however it did not give an accurate estimate of the regeneration efficiency. The small changes in GAC pore size distribution were consistent with the low electrochemical regeneration efficiencies. These low efficiencies appear to be related to the low reversibility of NOM adsorption and to pH-induced adsorbate desorption being the primary mechanism for this type of electrochemical regeneration system.     

Adsorption isotherms: illusive capacity and role of oxygen

This paper examines the influence of molecular oxygen on the adsorptive capacity of GAC. A new experimental procedure for determining adsorption isotherms is introduced. This procedure, denoted as “anaerobic”, differs from the currently used techniques, denoted as “aerobic”, in that oxygen is repeatedly purged from the test environment. The results show that the capacity of GAC for the retention of o-cresol can increase up to 3-fold in the presence of oxygen when compared to the anaerobic capacity. The same trend is observed for the adsorption of phenol and 3-ethylphenol. It is shown that this increase in capacity cannot be attributed to biological degradation of these adsorbates in the presence of oxygen. It is speculated that this phenomenon is due to some chemical reactions between the adsorbates and molecular oxygen that are catalyzed by the activated carbon surface and occur at a different time scale than physical adsorption. Initial portions of breakthrough curves for o-cresol are very accurately predicted using capacities depicted by the anaerobic isotherm, while the total GAC adsorptive capacity for o-cresol, as determined from breakthrough experiments, appears to agree closely with the capacity predicted from the aerobic isotherm.     

Elucidating competitive adsorption mechanisms of atrazine and NOM using model compounds

Based on the relative adsorbability of natural organic matter (NOM) fractions with different molecular weights (MWs), two model compounds, poly(styrene sulfonate) (PSS) (nominal MW=1800 Dalton) and p-dichlorobenzene (DCB), were chosen to study the competitive effect of large and small NOM molecules on atrazine adsorption by two powdered activated carbons (PACs) with different pore size distributions. Both isotherm and kinetic tests of atrazine adsorption were conducted using fresh PAC and PAC preloaded with the model compounds. The model compounds were found to affect atrazine adsorption through two different mechanisms due to their size difference: direct competition for sites by p-DCB and pore constriction/blockage by PSS-1.8k. p-DCB was found to significantly reduce atrazine adsorption capacity but to have no effect on atrazine adsorption kinetics. In contrast, the effect of PSS-1.8k on atrazine adsorption capacity was very small. Furthermore, during simultaneous adsorption, PSS-1.8k had no effect on atrazine surface diffusion. However, preloading PAC with PSS-1.8k lowered the atrazine surface diffusion coefficient, D(s), by more than three orders of magnitude; D(s) decreased with increasing solid phase PSS-1.8k concentration. The pore size distribution of the PAC was found to play an important role in competitive adsorption. A high mesopore surface area could alleviate pore blockage significantly.     

Adsorption of chlorinated organic compounds on activated carbon from water

The adsorption capacities and rates of seven principal chlorinated organic compounds for six commercial GACs were investigated. All the adsorption isotherms were expressed by the Freundlich equation, and the isotherms for the chloroethylenes such as trans - 1,2-dichloroethylene, trichloroethylene and tetrachloroethylene could be shown by the modified Freundlich equation Q′ = k′ (C/C_s)^l/n for each GAC. The magnitude of adsorption of the chlorinated organic compounds was in the order of: tetrachloroethylene > trichloroethylene > trans - 1,2-dichloroethylene > 1,1-dichloroethane > carbontetrachloride > 1.1,1-trichloroethane > chloroform. The value of k for a certain GAC could be predicted from the quantity of pores smaller than 2 nm in diameter. The adsorbed amounts were decreased by 10–20% when humic substances coexisted. The working periods of a fixed bed adsorber before regeneration were predicted by calculating breakthrough curves for various influent concentrations of trichloroethylene and tetrachloroethylene at the space velocities of 5 or 10 h⁻¹, and it was certified that the adsorption method by GAC was feasible for removing these compounds from water.     

Regeneration of acid orange 7-exhausted granular activated carbons with microwave irradiation

An investigation was performed for the regeneration of three granular activated carbons (GACs) exhausted with acid orange 7 (AO7). The three GACs were made from different materials, i.e. coconut shells, almond nucleus and coal. The AO7 adsorption process was carried out in a continuous-flow adsorption column. After adsorption, the AO7-saturated GAC was dried at 120 °C, then regenerated in a quartz reactor by 2450 MHz microwave (MW) irradiation at 850 W for 5 min. The efficacy of this procedure was analyzed by determining the rates and amounts of AO7 adsorbed in successive adsorption–MW regeneration cycles. Effects of this regeneration on the structural properties, surface chemistry and the AO7 adsorption capacities of GAC samples were examined. It was found that after several adsorption–MW regeneration cycles, the adsorption rates and capacities of GACs could maintain relatively high levels, even higher than those of virgin GACs, as indicated by AO7 breakthrough curves and adsorption isotherms. The improvement of GAC adsorption properties resulted from the modification of pore size distribution and surface chemistry by MW irradiation.     

Simultaneous uptake of anionic surfactants and micellar-solubilized contaminants using anion-exchange resins

This research studied simultaneous uptake of anionic surfactants and micellar-solubilized organic contaminants by anion-exchange resins. Anionic surfactant molecules adsorbed onto the positively charged resin mainly through electrostatic attraction, while the micellar-solubilized contaminants were excluded from aqueous solutions once the remaining micelles could no longer solubilize them. Data suggest that the excess contaminants adsorbed onto the resin skeleton and admicelle layer formed on the resin surface through hydrophobic interactions and eventually partitioned into the resin gel phase matrix. In batch adsorption, the contaminant solubilization capacity did not decrease linearly with respect to surfactant concentration decrease due to the increased solution counterion activity during anion exchange, and caused "delayed" contaminant uptake relative to that of the surfactant. No such effect occurred in continuous column adsorption, where the surfactant and contaminant breakthrough occurred simultaneously. Surfactant head and tail group properties, along with resin structure and particle size significantly affected surfactant and contaminant uptake rates. Relative to recovering the surfactant, the high exchange potential of the anionic surfactant prevented effective surfactant desorption, even at high electrolyte concentration and in the presence of a cosolvent. The resin matrix also had high affinity for the partitioned contaminant, and the contaminant elution from the resin seemed to be controlled by equilibrium partitioning.     

Adsorptive selenite removal from water using iron-coated GAC adsorbents

Removal of selenite from aqueous phase using iron-coated granular activated carbons (GAC) was investigated in this study. Five different types of GAC were used for iron coating by oxidizing ferrous chloride with sodium hypochlorite and the iron-coated GAC (Fe-GAC) were tested for selenite removal. Nitrogen adsorption-desorption analyses indicated that Brunauer-Emmett-Teller (BET) specific surface area, pore size, and pore volume decreased with the iron coating. The Darco 12x20 GAC was shown to be the most effective adsorbent among the five tested GACs after iron coating. Among the different concentrations used for iron coating, the Darco 12x20 GAC coated with 0.1M ferrous chloride achieved the highest selenite removal (97.3%). High removal efficiency of selenite occurred in a wide range of pH (i.e., 2-8), but the efficiency decreased when pH was higher than 8. Adsorption kinetics showed that selenite removal efficiency reached more than 90% after 6-h adsorption for initial selenium concentration of 2mg/L and equilibrium was obtained after 48h. A pseudo-second-order kinetic model was found to characterize the adsorption kinetics well for all the initial selenium concentrations and temperatures tested (R(2)>/=0.9969). Three temperatures (25, 35, 45 degrees C) were used to examine temperature effect on the adsorption behavior of the Fe-GAC with initial selenium concentration of 1mg/L. Activation energy was calculated to be 30.42kJ/mol. Adsorption isotherms for initial selenium concentration of 2mg/L at various temperatures and ionic strengths were developed and the data generally fit the Langmuir model well (R(2)>/=0.994). The adsorption capacity reached as high as 2.50mg-Se/g-adsorbent at equilibrium for initial concentration of 2mg/L at 25 degrees C. The Gibbs free energy was determined to be negative, indicating the spontaneous nature of the adsorption reaction. Oxyanion competitive adsorption showed that sulfate (0.1-5mM) barely affected selenite adsorption. Other anions (phosphate, silicate and carbonate) impact selenite adsorption to various degrees with phosphate completely excluded selenite adsorption at 5mM. The possible adsorption mechanisms were discussed.