Intraparticle diffusion and adsorption of arsenate onto granular ferric hydroxide (GFH)

Porous iron oxides are being evaluated and selected for arsenic removal in potable water systems. Granular ferric hydroxide, a typical porous iron adsorbent, is commercially available and frequently considered in evaluation of arsenic removal methods. GFH is a highly porous (micropore volume approximately 0.0394+/-0.0056 cm(3)g(-1), mesopore volume approximately 0.0995+/-0.0096 cm(3)g(-1)) adsorbent with a BET surface area of 235+/-8 m(2)g(-1). The purpose of this paper is to quantify arsenate adsorption kinetics on GFH and to determine if intraparticle diffusion is a rate-limiting step for arsenic removal in packed-bed treatment systems. Data from bottle-point isotherm and differential column batch reactor (DCBR) experiments were used to estimate Freundlich isotherm parameters (K and 1/n) as well as kinetic parameters describing mass transfer resistances due to film diffusion (k(f)) and intraparticle surface diffusion (D(s)). The pseudo-equilibrium (18 days of contact time) arsenate adsorption density at pH 7 was 8 microg As/mg dry GFH at a liquid phase arsenate concentration of 10 microg As/L. The homogeneous surface diffusion model (HSDM) was used to describe the DCBR data. A non-linear relationship (D(S)=3.0(-9) x R(p)(1.4)) was observed between D(s) and GFH particle radius (R(P)) with D(s) values ranging from 2.98 x 10(-12) cm(2)s(-1) for the smallest GFH mesh size (100 x 140) to 64 x 10(-11) cm(2)s(-1) for the largest GFH mesh size (10 x 30). The rate-limiting process of intraparticle surface diffusion for arsenate adsorption by porous iron oxides appears analogous to organic compound adsorption by activated carbon despite differences in adsorption mechanisms (inner-sphere complexes for As versus hydrophobic interactions for organic contaminants). The findings are discussed in the context of intraparticle surface diffusion affecting packed-bed treatment system design and application of rapid small-scale column tests (RSSCTs) to simulate the performance of pilot- or full-scale systems at the bench-scale.     

Defluoridation from aqueous solutions by granular ferric hydroxide (GFH)

This research was undertaken to evaluate the feasibility of granular ferric hydroxide (GFH) for fluoride removal from aqueous solutions. Batch experiments were performed to study the influence of various experimental parameters such as contact time (1 min-24 h), initial fluoride concentration (1-100 mg L⁻¹), temperature (10 and 25 °C), pH (3-12) and the presence of competing anions on the adsorption of fluoride on GFH. Kinetic data revealed that the uptake rate of fluoride was rapid in the beginning and 95% adsorption was completed within 10 min and equilibrium was achieved within 60 min. The sorption process was well explained with pseudo-first-order and pore diffusion models. The maximum adsorption capacity of GFH for fluoride removal was 7.0 mg g⁻¹. The adsorption was found to be an endothermic process and data conform to Langmuir model. The optimum fluoride removal was observed between pH ranges of 4-8. The fluoride adsorption was decreased in the presence of phosphate followed by carbonate and sulphate. Results from this study demonstrated potential utility of GFH that could be developed into a viable technology for fluoride removal from drinking water.     

Breakthrough behavior of granular ferric hydroxide (GFH) fixed-bed adsorption filters: modeling and experimental approaches

Breakthrough curves (BTC) for the adsorption of arsenate and salicylic acid onto granulated ferric hydroxide (GFH) in fixed-bed adsorbers were experimentally determined and modeled using the homogeneous surface diffusion model (HSDM). The input parameters for the HSDM, the Freundlich isotherm constants and mass transfer coefficients for film and surface diffusion, were experimentally determined. The BTC for salicylic acid revealed a shape typical for trace organic compound adsorption onto activated carbon, and model results agreed well with the experimental curves. Unlike salicylic acid, arsenate BTCs showed a non-ideal shape with a leveling off at c/c0 approximately 0.6. Model results based on the experimentally derived parameters over-predicted the point of arsenic breakthrough for all simulated curves, lab-scale or full-scale, and were unable to catch the shape of the curve. The use of a much lower surface diffusion coefficient D(S) for modeling led to an improved fit of the later stages of the BTC shape, pointing on a time-dependent D(S). The mechanism for this time dependence is still unknown. Surface precipitation was discussed as one possible removal mechanism for arsenate besides pure adsorption interfering the determination of Freundlich constants and D(S). Rapid small-scale column tests (RSSCT) proved to be a powerful experimental alternative to the modeling procedure for arsenic.     

Predicting anion breakthrough in granular ferric hydroxide (GFH) adsorption filters

Adsorption of arsenate, phosphate, salicylic acid, and groundwater DOC onto granular ferric hydroxide (GFH) was studied in batch and column experiments. Breakthrough curves were experimentally determined and modelled using the homogeneous surface diffusion model (HSDM) and two of its derivatives, the constant pattern homogeneous surface diffusion model (CPHSDM) and the linear driving force model (LDF). Input parameters, the Freundlich isotherm constants, and mass transfer coefficients for liquid- and solid-phase diffusion were determined and analysed for their influence on the shape of the breakthrough curve. HSDM simulation results predict the breakthrough of all investigated substances satisfactorily, but LDF and CPHSDM could not describe arsenate breakthrough correctly. This is due to a very slow intraparticle diffusion and hence higher Biot numbers. Based on this observation, limits of applicability were defined for LDF and CPHSDM. When designing fixed-bed adsorbers, model selection based on known or estimated Biot and Stanton numbers is possible.     

Advanced phosphorus removal from membrane filtrates by adsorption on activated aluminium oxide and granulated ferric hydroxide

The advanced phosphorus (P) removal by adsorption was studied for its suitability as a post-treatment step for membrane bioreactor (MBR) effluents low in P concentration and particle content. Two commercial adsorbents, granulated ferric hydroxide (GFH) and activated aluminium oxide (AA), were studied in batch tests and lab-scale filter tests for P adsorption in MBR filtrates. GFH showed a higher maximum capacity for phosphate and a higher affinity at low P concentrations compared to AA. Competition by inorganic ions was negligible for both adsorbents at the original pH (8.2). When equilibrium P concentrations exceeded 2 mg L(-1) in the spiked MBR filtrates, a precipitation of calcium phosphates occurred additionally to adsorption. During column studies the effluent criteria of 50 microgL(-1) P was reached after a throughput of 8000 bed volumes for GFH and 4000 for AA. Dissolved organic carbon appears to be the strongest competitor for adsorption sites. A partial regeneration and reloading of both adsorbents could be achieved by the use of sodium hydroxide.     

Hexavalent chromium removal from aqueous solution by adsorption on aluminum magnesium mixed hydroxide

A series of sols consisting of aluminum magnesium mixed hydroxide (AMH) nanoparticles with various Mg/Al molar ratios were prepared by coprecipitation. The use of AMH as adsorbent to remove Cr(VI) from aqueous solution was investigated. Adsorption experiments were carried out as a function of the Mg/Al molar ratio, pH, contact time, concentration of Cr(VI) and temperature. It was found that AMH with Mg/Al molar ratio 3 has the largest adsorption efficiency due to the smallest average particle diameter and the highest zeta potential; AMH was particularly effective for the Cr(VI) removal in a pH range from acid to slightly alkaline, even though the most effective pH range was between 2.5 and 5.0. The adsorption of Cr(VI) on AMH reached equilibrium within 150 min. The saturated adsorption capacities of AMH for Cr(VI) were 105.3-112.0 mg/g at 20-40 °C. The interaction between the surface sites of AMH and the Cr(VI) ions may be a combination of both anion exchange and surface complexation. The pseudo-second-order model best described the adsorption kinetics of Cr(VI) onto AMH. The results showed that AMH can be used as a new adsorbent for Cr(VI) removal which has higher adsorption capacity and faster adsorption rate at pH values close to that at which pollutants are usually found in the environment.     

NOM removal by adsorption onto granular ferric hydroxide: Equilibrium, kinetics, filter and regeneration studies

Adsorption onto granular ferric hydroxide (GFH) with subsequent in-situ regeneration is studied as a new process for natural organic matter (NOM) removal from groundwater. Adsorbent equilibrium loadings of 10-30 mgDOC g(-1)GFH(-1) are obtained, whereas the non-adsorbable DOC fraction amounts to 1.5 mgL(-1) for all investigated groundwaters. The larger and UV-active NOM fractions (mainly fulvic acids) are well adsorbed while the smaller molecular fractions are poorly or not adsorbed. However, kinetic studies show that the smaller and medium-sized fulvic acids are removed first. The equilibrium is strongly dependent on pH but only weakly on ionic strength, pointing to ligand exchange as the dominant adsorption mechanism. With regard to NOM structure, prerequisites for adsorption onto GFH are both a minimum number of functional groups and a molecular size small enough to enter the GFH pores. NOM breakthrough curves are successfully simulated using the LDF model (homogeneous surface diffusion model (HSDM) with linear driving force approach for surface diffusion) and experimentally determined mass transfer coefficients. Regeneration of loaded GFH is possible either by use of NaOH or oxidatively by H(2)O(2). The optimal quantities and concentrations are determined.     

Removal of arsenic (III) and arsenic (V) from aqueous medium using chitosan-coated biosorbent

A biosorbent was prepared by coating ceramic alumina with the natural biopolymer, chitosan, using a dip-coating process. Removal of arsenic (III) (As(III)) and arsenic (V) (As(V)) was studied through adsorption on the biosorbent at pH 4.0 under equilibrium and dynamic conditions. The equilibrium adsorption data were fitted to Langmuir, Freundlich, and Redlich-Peterson adsorption models, and the model parameters were evaluated. All three models represented the experimental data well. The monolayer adsorption capacity of the sorbent, as obtained from the Langmuir isotherm, is 56.50 and 96.46 mg/g of chitosan for As(III) and As(V), respectively. The difference in adsorption capacity for As(III) and As(V) was explained on the basis of speciation of arsenic at pH 4.0. Column adsorption results indicated that no arsenic was found in the effluent solution up to about 40 and 120 bed volumes of As(III) and As(V), respectively. Sodium hydroxide solution (0.1M) was found to be capable of regenerating the column bed.     

Removal of quinol from aqueous solution by adsorption onto Fe(III)/Cr(III) hydroxide and application to real effluent treatment

The adsorption capacity of ‘waste’ Fe(III)/Cr(III) hydroxide for removal of quinol at varying agitation time, quinol concentration, adsorbent dose, pH and temperature was investigated by batch method. The Langmuir isotherm was found to represent the equilibrium sorption data well and the adsorption capacity was found to be 24.4 mg g^?1 and 28.2 mg g^?1 for untreated and pre‐treated adsorbent, respectively. Adsorption followed second‐order kinetics. Adsorption was maximum and uniform in the pH range 4.0–10.0 and 6.0–10.0 for untreated and pre‐treated adsorbent, respectively. The adsorption was endothermic in nature. Application of the adsorbent to the treatment of real effluent was demonstrated.     

Chemical reactions between arsenic and zero-valent iron in water

Batch experiments and X-ray photoelectron spectroscopic (XPS) analyses were performed to study the reactions between arsenate [As(V)], arsenite [As(III)] and zero-valent iron [Fe(0)]. The As(III) removal rate was higher than that for As(V) when iron filings (80-120 mesh) were mixed with arsenic solutions purged with nitrogen gas in the pH range of 4-7. XPS spectra of the reacted iron coupons showed the reduction of As(III) to As(0). Soluble As(III) was formed when As(V) reacted with Fe(0) under anoxic conditions. However, no As(0) was detected on the iron coupons after 5 days of reaction in the As(V)-Fe(0) system. The removal of the arsenic species by Fe(0) was attributed to electrochemical reduction of As(III) to sparsely soluble As(0) and adsorption of As(III) and As(V) to iron hydroxides formed on the Fe(0) surface under anoxic conditions. When the solutions were open to atmospheric air, the removal rates of As(V) and As(III) were much higher than under the anoxic conditions, and As(V) removal was faster than As(III). The rapid removal of As(III) and As(V) was caused by adsorption on ferric hydroxides formed readily through oxidation of Fe(0) by dissolved oxygen.     

Mechanism of phenol adsorption onto electro-activated carbon granules

The main purpose of this paper is to determine the mechanisms which govern the adsorption of the phenol onto electro-activated carbon granules. This new activation technique allowed an increase of the performance of the adsorbent. Two models were utilised to understand the improvement in the performance of electroactivated carbon granules. The first, a simple external resistance model based on film resistance, gave acceptable predictions, with an error of less than 15%, between the theoretical results and experimental data independent of the activation potential and phenol initial concentration. The second linear model, based on diffusion phenomena, was more representative in describing the experiment than the first model. It was observed that the electro-activation method did not change the mechanism which governs phenol adsorption onto granular carbon. Indeed, the same mathematical model based on diffusion phenomena made it possible to predict with a very low error (less than 5%) the experimental data obtained for the favourable activation potential, without activation potential and with an unfavourable activation potential. The electro-activation technique makes it possible to increase the number of active sites that improve the performance of the electro-activated granular carbon compared with conventional granular activated carbon.     

Kinetic analysis for the removal of a reactive dye from aqueous solution onto hydrotalcite by adsorption

The removal of a reactive color, Cibacron Yellow LS-R, from aqueous solutions by adsorption onto hydrotalcite particles is investigated using batch rate experiments. Measurements are performed at various initial color concentrations, solid loads, pH values and ionic backgrounds (dissolved NaCl). The speed of agitation and the temperature inside the batch adsorber are also varied within a practical range of values. It is shown that the sorption capacity is relatively high for most experimental conditions so hydrotalcite may be considered as a suitable sorbent for this application. The probable mechanism of the process is investigated by a number of homogeneous and heterogeneous reaction kinetic models as well as diffusion kinetic models. It is found that no single kinetic model can fully describe the sorption process at all times. At least three independent rate-controlling mechanisms appear to compete each other and dominate the different stages of sorption.     

Kinetics of a reactive dye adsorption onto dolomitic sorbents

A novel wastewater treatment technique has been investigated, for reactive dye removal, in batch kinetic systems. These experimental studies have indicated that charred dolomite has the potential to act as an adsorbent for the removal of Brilliant Red reactive dye from aqueous solution. The effect of initial dye concentration, adsorbent mass:liquid volume ratio, and agitation speed on dye removal have been determined with the experimental data mathematically described using empirical external mass transfer and intra-particle diffusion models. The experimental data show conformity with an adsorption process, with the removal rate heavily dependent on both external mass transfer and intra-particle diffusion.     

Ammonium adsorption in aerobic granular sludge, activated sludge and anammox granules

The ammonium adsorption properties of aerobic granular sludge, activated sludge and anammox granules have been investigated. During operation of a pilot-scale aerobic granular sludge reactor, a positive relation between the influent ammonium concentration and the ammonium adsorbed was observed. Aerobic granular sludge exhibited much higher adsorption capacity compared to activated sludge and anammox granules. At an equilibrium ammonium concentration of 30 mg N/L, adsorption obtained with activated sludge and anammox granules was around 0.2 mg NH₄-N/g VSS, while aerobic granular sludge from lab- and pilot-scale exhibited an adsorption of 1.7 and 0.9 mg NH₄-N/g VSS, respectively. No difference in the ammonium adsorption was observed in lab-scale reactors operated at different temperatures (20 and 30 °C). In a lab-scale reactor fed with saline wastewater, we observed that the amount of ammonium adsorbed considerably decreased when the salt concentration increased. The results indicate that adsorption or better ion exchange of ammonium should be incorporated into models for nitrification/denitrification, certainly when aerobic granular sludge is used.     

Competitive adsorption of phosphate and phosphonates onto goethite

Phosphate and phosphonates are both strongly adsorbed onto mineral surfaces and their removal during wastewater treatment is mainly due to adsorptive processes. We have conducted experiments to study the mutual influence of phosphate and six different phosphonates on each other in buffered medium at pH 7.2. We have used phosphonates having one to five phosphonic acid groups (HMP, IDMP, HEDP, NTMP, EDTMP and DTPMP). The presence of phosphonates suppressed the adsorption of phosphate. The monophosphonate HMP had the smallest and the polyphosphonates the largest effect on phosphate adsorption. The presence of phosphate lowered phosphonate adsorption. The competition in the multicomponent system can reasonably well be predicted using a surface complexation model developed for single component systems. The competitive model only failed in systems containing the polyphosphonate DTPMP. With this approach we can predict the behavior of both compounds during wastewater treatment. The calculations show that phosphonates have a small effect on phosphate adsorption at the actual concentrations in observed wastewater. Adsorption of low concentrations of phosphonates was calculated to be significantly reduced by phosphate concentrations as observed in wastewater.     

pH-dependent effect of zinc on arsenic adsorption to magnetite nanoparticles

The effect of Zn²⁺ on both the kinetic and equilibrium aspects of arsenic adsorption to magnetite nanoparticles was investigated at pH 4.5-8.0. At pH 8.0, adsorption of both arsenate and arsenite to magnetite nanoparticles was significantly enhanced by the presence of small amount of Zn²⁺ in the solution. With less than 3 mg/L of Zn²⁺ added to the arsenic solution prior to the addition of magnetite nanoparticles, the percentage of arsenic removal by magnetite nanoparticles increased from 66% to over 99% for arsenate, and from 80% to 95% for arsenite from an initial concentration of ∼100 μg/L As at pH 8.0. Adsorption rate also increased significantly in the presence of Zn²⁺. The adsorption-enhancement effect of Zn²⁺ was not observed at pH 4.5-6.0, nor with ZnO nanoparticles, nor with surface-coated Zn-magnetite nanoparticles. The enhanced arsenic adsorption in the presence of Zn²⁺ cannot be due to reduced negative charge of the magnetite nanoparticles surface by zinc adsorption. Other cations, such as Ca²⁺ and Ag⁺, failed to enhance arsenic adsorption. Several potential mechanisms that could have caused the enhanced adsorption of arsenic have been tested and ruled out. Formation of a ternary surface complex by zinc, arsenic and magnetite nanoparticles is a possible mechanism controlling the observed zinc effect. Zinc-facilitated adsorption provides further advantage for magnetite nanoparticle-enhanced arsenic removal over conventional treatment approaches.

Synopsis

Arsenic adsorption to magnetite nanoparticles at neutral or slightly basic pH can be significantly enhanced with trace amount of Zn²⁺ due to the formation of a ternary complex.     

Performance of granular zirconium-iron oxide in the removal of fluoride from drinking water

In this study, a granular zirconium-iron oxide (GZI) was successfully prepared using the extrusion method, and its defluoridation performance was systematically evaluated. The GZI was composed of amorphous and nano-scale oxide particles. The Zr and Fe were evenly distributed on its surface, with a Zr/Fe molar ratio of ∼2.3. The granular adsorbent was porous with high permeability potential. Moreover, it had excellent mechanical stability and high crushing strength, which ensured less material breakage and mass loss in practical use. In batch tests, the GZI showed a high adsorption capacity of 9.80 mg/g under an equilibrium concentration of 10 mg/L at pH 7.0, which outperformed many other reported granular adsorbents. The GZI performed well over a wide pH range, of 3.5-8.0, and especially well at pH 6.0-8.0, which was the preferred range for actual application. Fluoride adsorption on GZI followed pseudo-second-order kinetics and could be well described by the Freundlich equilibrium model. With the exception of HCO₃⁻, other co-existing anions and HA did not evidently inhibit fluoride removal by GZI when considering their real concentrations in natural groundwater, which showed that GZI had a high selectivity for fluoride. In column tests using real groundwater as influent, about 370, 239 and 128 bed volumes (BVs) of groundwater were treated before breakthrough was reached under space velocities (SVs) of 0.5, 1 and 3 h⁻¹, respectively. Additionally, the toxicity characteristic leaching procedure (TCLP) results suggested that the spent GZI was inert and could be safely disposed of in landfill. In conclusion, this granular adsorbent showed high potential for fluoride removal from real groundwater, due to its high performance and physical-chemical properties.     

Removal of arsenic from contaminated water sources by sorption onto iron-oxide-coated polymeric materials

The modification of polymeric materials (polystyrene and polyHIPE) by coating their surface with appropriate adsorbing agents (i.e. iron hydroxides) was investigated in the present work, in order to apply the modified media in the removal of inorganic arsenic anions from contaminated water sources. The method, termed adsorptive filtration, has been classified as an emerging technology in water treatment processes as it presents several advantages towards conventional technologies: the production of high amounts of toxic sludge can be avoided and it is considered as economically more efficient; whereas it has not yet been applied in full-scale treatment plants for low-level arsenic removal. The present experiments showed that both modified media were capable in removing arsenic from the aqueous stream, leading to residual concentration of this toxic metalloid element below 10 μg/L, which is the new maximum concentration limit set recently by the European Commission and imposed by the USEPA. Though, among the examined materials, polyHIPE was found to be more effective in the removal of arsenic, as far as it concerns the maximum sorptive capacity before the filtration bed reaches the respective breakthrough point.     

Evaluation of metal hydroxide sludge for reactive dye adsorption in a fixed-bed column system

The capacity and performance of small-scale column, containing coarse particles of metal hydroxide sludge, were evaluated using 30mgl(-1) dye solutions of C.I. Reactive Red 141. The studied bed depths were 2.5-20cm and the studied flow rates were 1.1, 2.2 and 3.3mlmin(-1)cm(-2). At the breakthrough point of 0.1C(t)/C(0), the breakthrough volume was increased with increasing bed depth or decreasing flow rate, due to an increase in empty bed contact time (EBCT). The data followed the bed depth service time model, and the adsorption capacity was 24-26mgcm(-3) or 27-29mgdyesg(-1) adsorbent. The minimum bed depths should be higher 1.02, 2.04 and 2.59cm with flow rates of 1.1, 2.2 and 3.3mlmin(-1)cm(-2), respectively, while the ratio of bed depth to diameter should not be higher than 6. With EBCT above 5min, the usage rate of metal hydroxide sludge was 1.3gl(-1). Using the bed depth of 5cm and the flow rate of 0.55mlmin(-1)cm(-2), 87% of dominant colour, 78% of COD, and 99% of SS could be removed from the textile wastewater, and the leachate of toxic heavy metals was under the standard limitations.     

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.