Characterization of natural organic matter adsorption in granular activated carbon adsorbers

The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.     

Anchorage of iron hydro(oxide) nanoparticles onto activated carbon to remove As(V) from water

The adsorption of arsenic (V) by granular iron hydro(oxides) has been proven to be a reliable technique. However, due to the low mechanical properties of this material, it is difficult to apply it in full scale water treatment. Hence, the aim of this research is to develop a methodology to anchor iron hydro(oxide) nanoparticles onto activated carbon, in which the iron hydro(oxide) nanoparticles will give the activated carbon an elevated active surface area for arsenic adsorption and also help avoid the blockage of the activated carbon pores. Three activated carbons were modified by employing the thermal hydrolysis of iron as the anchorage procedure. The effects of hydrolysis temperature (60-120 °C), hydrolysis time (4-16 h), and FeCl₃ concentration (0.4-3 mol Fe/L) were studied by the surface response methodology. The iron content of the modified samples ranged from 0.73 to 5.27%, with the higher end of the range pertaining to the carbons with high oxygen content. The materials containing smaller iron hydro(oxide) particles exhibited an enhanced arsenic adsorption capacity. The best adsorbent material reported an arsenic adsorption capacity of 4.56 mg As/g at 1.5 ppm As at equilibrium and pH 7.     

Single and competitive adsorption of Cd and Zn onto a granular activated carbon

Single and competitive adsorption of cadmium and zinc onto granular activated carbon DARCO 12–20 mesh has been investigated. This activated carbon has been shown as an effective adsorbent for both metals. Cadmium and zinc removals increased with pH and decreased with molar metal/carbon ratio. Surface precipitation phenomena have been detected for the higher pHs and molar ratios. The adsorption process has been modelled on the surface complexation Triple Layer Model (TLM). For this purpose, the amphoteric nature of the activated carbon has been studied. Single metal adsorption data have been used to calibrate TLM parameters. A dependence of the adsorption constants on pH and molar metal/carbon ratio has been observed, and a correlation for log K_ads has been determined. In the competitive system, the removal efficiency of the activated carbon decreased for both metals. The TLM model, using surface complexation constants determined from single adsorption experiments, successfully predicted cadmium and zinc removal from the two metal solutions.     

活性炭吸附去除重金属研究进展

介绍了国内外学者应用活性炭吸附去除包括:Cr(Ⅵ),Cu2 ,Zn2 ,Cd2 ,Pb2 ,Mn2 ,Hg2 以及混合重金属离子在内的各种废水的处理效果与影响因素,并对相应的吸附机理进行了讨论,以促进活性炭吸附去除重金属离子的进展。     

Modeling As(V) removal by a iron oxide impregnated activated carbon using the surface complexation approach

The objective of this research was to model As(V) removal onto a iron oxide impregnated activated carbon (FeAC) using the surface complexation model (SCM) approach. As(V) removal by FeAC was due to the impregnated Fe oxide, not the base carbon material and was a strong function of pH. The two-monoprotic site-triple layer model adequately described As(V) removal using 2 fitting parameters compared with the 3 parameters needed for the diprotic site model. This, along with a better representation of the recognized As(V) removal mechanism (ligand exchange with -OH) as well as the acid-base behavior makes the two-monoprotic approach the better model for As(V) removal by the impregnated iron oxide although the diprotic model was able to describe the pH dependent removal of As(V). Both models were also able to predict As(V) removal at different adsorbent/adsorbate ratios using K(As) determined from a single FeAC adsorption experiment. Thus, fewer adsorption experiments are required in order to model As(V) removal in equilibrium and column systems. The results described in this work will be used as a foundation in developing a dynamic model to predict As(V) adsorption in a fixed-bed adsorber.     

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.     

Adsorption of Sevin and Baygon on granular activated carbon

Adsorption of Sevin and Baygon on granular activated carbon was investigated. Adsorption parameters of Freundlich and Langmuir isotherms are useful indications of the adsorption capacity of carbon and the anticipated sharpness of breakthrough front. Adsorption of tested carbamates depends on their chemical structure and branching of the side chains. Contact time tends to be the most important factor controlling the efficiency of the adsorption process and a linear relationship was obtained between the logarithm of contact time and volume of effluent passing the column before breakthrough of Sevin.     

Economical and ecological comparison of granular activated carbon (GAC) adsorber refill strategies

Technical constraints can leave a considerable freedom in the design of a technology, production or service strategy. Choosing between economical or ecological decision criteria then characteristically leads to controversial solutions of ideal systems. For the adaptation of granular-activated carbon (GAC) fixed beds, various technical factors determine the adsorber volume required to achieve a desired service life. In considering carbon replacement and recycling, a variety of refill strategies are available that differ in terms of refill interval, respective adsorber volume, and time-dependent use of virgin, as well as recycled GAC. Focusing on the treatment of contaminant groundwater, we compare cost-optimal reactor configurations and refill strategies to the ecologically best alternatives. Costs and consumption of GAC are quantified within a technical-economical framework. The emissions from GAC production out of hard coal, transport and recycling are equally derived through a life cycle impact assessment. It is shown how high discount rates lead to a preference of small fixed-bed volumes, and accordingly, a high number of refills. For fixed discount rates, the investigation reveals that both the economical as well as ecological assessment of refill strategies are especially sensitive to the relative valuation of virgin and recycled GAC. Since recycling results in economic and ecological benefits, optimized systems thus may differ only slightly.     

颗粒活性炭吸附对预臭氧后微污染原水水质影响研究

在不同的预臭氧浓度条件下处理微污染原水,考察了颗粒活性灰（GAC）吸附对处理后水样水质的影响.选择化学需氧量（CODMn）、溶解性有机碳（DOC）、生物可降解溶解性有机碳（BDOC）、UV254和氨氮（NH;-N）含量及有机物分子量分布作为考察吸附效果的检测指标.结果表明,在静态吸附时间达到5天时,颗粒活性炭吸附曲线开始趋于平缓,吸附时间超过5天之后吸附趋于饱和;预臭氧含量为2.5 mg/L时,颗粒活性炭对有机物的吸附效果最佳,对CODMn、DOC、BDOC的去除率分别为53.2％,63.2％和36.2％;在不同预臭氧处理条件下,颗粒活性炭对NH;-N的吸附效果并未表现出较大的差异,吸附去除率约为5％;颗粒活性炭优先吸附水中分子量＞ 10kDa的有机物,其次为分子量＜1 kDa的有机物.     

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.     

Branched pore kinetic model analysis of geosmin adsorption on super-powdered activated carbon

Super-powdered activated carbon (S-PAC) is activated carbon of much finer particle size than powdered activated carbon (PAC). Geosmin is a naturally occurring taste and odor compound that impairs aesthetic quality in drinking water. Experiments on geosmin adsorption on S-PAC and PAC were conducted, and the results using adsorption kinetic models were analyzed. PAC pulverization, which produced the S-PAC, did not change geosmin adsorption capacity, and geosmin adsorption capacities did not differ between S-PAC and PAC. Geosmin adsorption kinetics, however, were much higher on S-PAC than on PAC. A solution to the branched pore kinetic model (BPKM) was developed, and experimental adsorption kinetic data were analyzed by BPKM and by a homogeneous surface diffusion model (HSDM). The HSDM describing the adsorption behavior of geosmin required different surface diffusivity values for S-PAC and PAC, which indicated a decrease in surface diffusivity apparently associated with activated carbon particle size. The BPKM, consisting of macropore diffusion followed by mass transfer from macropore to micropore, successfully described the batch adsorption kinetics on S-PAC and PAC with the same set of model parameter values, including surface diffusivity. The BPKM simulation clearly showed geosmin removal was improved as activated carbon particle size decreased. The simulation also implied that the rate-determining step in overall mass transfer shifted from intraparticle radial diffusion in macropores to local mass transfer from macropore to micropore. Sensitivity analysis showed that adsorptive removal of geosmin improved with decrease in activated carbon particle size down to 1 μm, but further particle size reduction produced little improvement.     

Adsorption of soluble aromatic hydrocarbons on granular activated carbon

Adsorption of benzene, toluene, o-oxylene and ethylbenzene on granular activated carbon proceeds in accordance with the Freundlich model. Adsorption parameters, k and 1/n, reflect the effects of chemical structure, solubility and competitive interactions on the adsorption process. Results obtained add to the validity of the carbon column technique in the removal of soluble aromatic hydrocarbons that affect water quality.     

Reversibility of adsorption of aromatic compounds onto powdered activated carbon (PAC)

Desorption of sorbed compounds is an important process in the powdered activated carbon-activated sludge (PAC-AS) wastewater treatment system, where sorption and biodegradation interact. To assess the extent of desorption to be expected in the PAC-AS system, reversibility of adsorption was investigated using isotherm studies and a leaching technique under the conditions prevalent in the PAC-AS system. Two aromatic compounds, o-cresol and 3-chlorobenzoic acid (3-CB), and two types of powdered activated carbon (PAC) were used to study desorption. High degrees of irreversible adsorption were observed with both desorption techniques, depending on the type of PAC and the compound. The thermally activated, peat-based PAC (SA4) showed a high degree of irreversible adsorption compared to the chemically activated, wood-derived PAC (CA1). The phenolic compound, o-cresol, could be desorbed to a lesser extent than 3-CB from both types of PAC. Contact time between the PAC and the compound was found to affect the desorption of o-cresol adversely. Oxygen availability enhanced the adsorptive capacity of SA4 for o-cresol. Sorption of 3-CB proved unaffected by either contact time or oxygen. Oxidative polymerization as a probable mechanism for the irreversible adsorption observed is also discussed. Desorption kinetics from SA4 showed a first phase of rapid desorption followed by a second phase of slow desorption. CA1 displayed the first rapid desorption phase only.     

Removal of As(III) and As(V) by Tin(II) compounds

The retention capacity for arsenic species of new nanomaterials based on tin(II) inorganic oxides or hybrid (inorganic and organic) materials was studied. The synthesis of a polymer-metal complex was performed with poly(acrylic acid) and tin(II) chloride. Poly(AA)-Sn(II) with 10 and 20 wt% of tin and a structure with a mol ratio tin:carboxylate group of 1:1, were characterized. These compounds with 10 and 20 wt% of tin content were used to compare the arsenic removal capability through the liquid-phase polymer-based retention, (LPR), technique. Also, tin oxide was prepared by adding alkaline solution to tin(II) chloride salt. The intermediate tin compound was studied by UV-Vis spectroscopy at different pH values and quantified by potentiometric titration. The solid structure is characterized by Fourier transformed infrared spectroscopy, X-ray diffraction, and specific area BET (N₂). Removal of arsenite and arsenate species from solution by hydrolysated tin was carried out by LPR technique with ultrafiltration membranes and a fixed-bed column unsupported or supported on SiO₂. In all these cases, a washing method at constant pH was applied. The arsenic retention ability depended on the class of tin compounds prepared, with a higher efficiency for arsenic being observed at basic pH for soluble complex poly(AA)-Sn(II) than that for tin hydroxide or hydrolysate of Sn⁺².     

Rapid and direct estimation of active biomass on granular activated carbon through adenosine tri-phosphate (ATP) determination

Granular activated carbon (GAC) filtration is used during drinking water treatment for the removal of micropollutants such as taste and odour compounds, halogenated hydrocarbons, pesticides and pharmaceuticals. In addition, the active microbial biomass established on GAC is responsible for the removal of biodegradable dissolved organic carbon compounds present in water or formed during oxidation (e.g., ozonation and chlorination) processes. In order to conduct correct kinetic evaluations of DOC removal during drinking water treatment, and to assess the state and performance of full-scale GAC filter installations, an accurate and sensitive method for active biomass determination on GAC is required. We have developed a straight-forward method based on direct measurement of the total adenosine tri-phosphate (ATP) content of a GAC sample and other support media. In this method, we have combined flow-cytometric absolute cell counting and ATP analysis to derive case-specific ATP/cell conversion values. In this study, we present the detailed standardisation of the ATP method. An uncertainty assessment has shown that heterogeneous colonisation of the GAC particles makes the largest contribution to the combined standard uncertainty of the method. The method was applied for the investigation of biofilm formation during the start-up period of a GAC pilot-scale plant treating Lake Zurich water. A rapid increase in the biomass of up to 1.1 x 10(10)cells/g GAC dry weight (DW) within the first 33 days was observed, followed by a slight decrease to an average steady-state concentration of 7.9 x 10(9)cells/g GAC DW. It was shown that the method can be used to determine the biomass attached to the GAC for both stable and developing biofilms.     

Adsorption of As(V) and As(III) by nanocrystalline titanium dioxide

This study evaluated the effectiveness of nanocrystalline titanium dioxide (TiO(2)) in removing arsenate [As(V)] and arsenite [As(III)] and in photocatalytic oxidation of As(III). Batch adsorption and oxidation experiments were conducted with TiO(2) suspensions prepared in a 0.04 M NaCl solution and in a challenge water containing the competing anions phosphate, silicate, and carbonate. The removal of As(V) and As(III) reached equilibrium within 4h and the adsorption kinetics were described by a pseudo-second-order equation. The TiO(2) was effective for As(V) removal at pH<8 and showed a maximum removal for As(III) at pH of about 7.5 in the challenge water. The adsorption capacity of the TiO(2) for As(V) and As(III) was much higher than fumed TiO(2) (Degussa P25) and granular ferric oxide. More than 0.5 mmol/g of As(V) and As(III) was adsorbed by the TiO(2) at an equilibrium arsenic concentration of 0.6mM. The presence of the competing anions had a moderate effect on the adsorption capacities of the TiO(2) for As(III) and As(V) in a neutral pH range. In the presence of sunlight and dissolved oxygen, As(III) (26.7 microM or 2mg/L) was completely converted to As(V) in a 0.2g/L TiO(2) suspension through photocatalytic oxidation within 25 min. The nanocrystalline TiO(2) is an effective adsorbent for As(V) and As(III) and an efficient photocatalyst.     

Adsorption of basic dyes on granular activated carbon and natural zeolite

The adsorption of basic dyes from aqueous solution onto granular activated carbon and natural zeolite has been studied using an agitated batch adsorber. The influence of agitation, initial dye concentration and adsorbent mass has been studied. The parameters of Langmuir and Freundlich adsorption isotherms have been determined using the adsorption data. Homogeneous diffusion model (solid diffusion) combined with external mass transfer resistance is proposed for the kinetic investigation. The dependence of solid diffusion coefficient on initial concentration and mass adsorbent is represented by the simple empirical equations.     

Pentachlorophenol adsorption and desorption characteristics of granular activated carbon-II. Kinetics

The kinetics of pentachlorophenol (PCP) adsorption/desorption with Calgon F300 granular activated carbon (GAC) was studied. A previously-developed model of GAC adsorption/desorption kinetics was applied to the case of PCP for both batch and continuous plug-flow liquid conditions. The model predictions were found to be in good agreement with the experimental observations.