César Valderrama

Sorption kinetics of polycyclic aromatic hydrocarbons removal using granular activated carbon: Intraparticle diffusion coefficients

Granular activated carbon (GAC) was evaluated as a suitable sorbent for polycyclic aromatic hydrocarbons (PAHs) removal from aqueous solutions. For this purpose, kinetic measurements on the extraction of a family of six PAHs were taken. A morphology study was performed by means of a scanning electron microscopy (SEM) analysis of GAC samples. Analyses of the batch rate data for each PAH were carried out using two kinetic models: the homogenous particle diffusion model (HPDM) and the shell progressive model (SPM). The process was controlled by diffusion rate the solutes (PAHs) that penetrated the reacted layer at PAH concentrations in the range of 0.2-10 mg L(-1). The effective particle diffusion coefficients (D(eff)) derived from the two models were determined from the batch rate data. The Weber and Morris intraparticle diffusion model made a double contribution to the surface and pore diffusivities in the sorption process. The D(eff) values derived from both the HPMD and SPM equations varied from 1.1 x 10(-13) to 6.0 x 10(-14) m(2) s(-1). The simplest model, the pore diffusion model, was applied first for data analysis. The model of the next level of complexity, the surface diffusion model, was applied in order to gain a deeper understanding of the diffusion process. This model is able to explain the data, and the apparent surface diffusivities are in the same order of magnitude as the values for the sorption of functionalized aromatic hydrocarbons (phenols and sulphonates) that are described in the literature.

Phenol removal from aqueous solution by adsorption and ion exchange mechanisms onto polymeric resins

The removal of phenol from aqueous solution was evaluated by using a nonfunctionalized hyper-cross-linked polymer Macronet MN200 and two ion exchange resins, Dowex XZ (strong anion exchange resin) and AuRIX 100 (weak anion exchange). Equilibrium experimental data were fitted to the Langmuir and Freundlich isotherms at different pHs. The Langmuir model describes successfully the phenol removal onto the three resins. The extent of the phenol adsorption was affected by the pH of the solution; thus, the nonfunctionalized resin reported the maximum loading adsorption under acidic conditions, where the molecular phenol form predominates. In contrast both ion exchange resins reported the maximum removal under alkaline conditions where the phenolate may be removed by a combined effect of both adsorption and ion exchange mechanisms. A theoretical model proposed in the literature was used to fit the experimental data and a double contribution was observed from the parameters obtained by the model. Kinetic experiments under different initial phenol concentrations and under the best pH conditions observed in the equilibrium experiments were performed. Two different models were used to define the controlling mechanism of the overall adsorption process: the homogeneous particle diffusion model and the shell progressive model fit the kinetic experimental data and determined the resin phase mechanism as the rate-limiting diffusion for the phenol removal. Resins charged after the kinetic experiments were further eluted by different methods. Desorption of nonfunctionalized resin was achieved by using the solution (50% v/v) of methanol/water with a recovery close to 90%. In the case of the ion exchange resins the desorption process was performed at different pHs and considering the effect of the competitive ion Cl-. The desorption processes were controlled by the ion exchange mechanism for Dowex XZ and AuRIX 100 resins; thus, no significant effect for the addition of Cl- under acidic conditions was observed, while under alkaline conditions the total recovery increased, specially for Dowex XZ resin.

Modelling of the Ni(II) removal from aqueous solutions onto grape stalk wastes in fixed-bed column.

Grape stalk wastes generated in the wine production process were used for the removal of nickel (II) from aqueous solution. The experimental breakthrough curves were obtained in fixed-bed columns. Experiments we carry out in order to evaluate the influence of inlet metal concentration (30 and 70 mg L(-1)) and the regeneration process in a double sorption cycle. The CXTFIT code was used to fit the experimental data and to determine the transport and sorption parameters of the convective-dispersive equation (CDE) and the two-site deterministic non-equilibrium (TSM/CDE) model by adjusting the models to the experimental breakthrough curves (BTC). The results showed that bed capacity as well as transport and sorption parameters were affected by the initial metal concentration, at the highest Ni(II) concentration the grape stalks column saturated quickly leading to earlier breakthrough. The sorption capacity of the sorbent was slightly reduced in a double sorption cycle, while the recovery of the metal in the desorption step was ranging between 80% and 85% in both cycles.

Evaluation of Selective Sorbents for the Extraction of Valuable Metal Ions (Cs, Rb, Li, U) from Reverse Osmosis Rejected Brine

Abstract Three commercially available sorbents/exchangers (namely CsTreat, ZrP, and S910) were evaluated under column conditions for the extraction of four metals (Cs(I), Rb(I), Li(I), and U(VI)) from a brine rejected by a Seawater Reverse Osmosis plant. From the obtained breakthrough curves and periodic analysis of the influent and effluent, the uptake capacities of the materials were quantified. The fixation of the target metal onto the sorbents was investigated also by SEM-EDX and FTIR-ATR analysis. The results showed that CsTreat displayed a high sorption capacity of Rb(I) and a fairly high sorption capacity of Cs(I), as the resin S910 showed of U(VI), while ZrP proved to be ineffective for the retention of Li(I).

Reactive transport of arsenic(III) and arsenic(V) on natural hematite: experimental and modeling.

Natural hematite was used for the removal of arsenic(III) and arsenic(V) from aqueous solution. The experimental breakthrough curves were obtained in fixed-bed columns. The transport of arsenic in a simplified fixed-bed configuration was quantified by using the CXTFIT code, which was used to estimate the transport and sorption parameters of the convective-dispersive equation (CDE) and the two-site deterministic nonequilibrium (TSM/CDE) model by fitting the models to the experimental breakthrough curves (BTC). The prediction of the breakthrough curves performed by the two-site nonequilibrium sorption model resulted in a good fit, indicating that this model can properly describe the transport and sorption processes of arsenic on natural hematite. Additionally the parameters obtained indicate that nonequilibrium sorption governs the As(III) and As(V) uptake onto hematite in a fixed-bed column. No significant differences in the transport and sorption parameters of As(III) and As(V) on natural hematite were obtained; the retardation factor values were in the same order of magnitude for both species.

Cr(III) removal from aqueous solutions: A straightforward model approaching of the adsorption in a fixed-bed column

Prediction of breakthrough curves for continuous sorption characterization is generally performed by means of simple and simplified equations. These expressions hardly have any physical meaning and, also do not allow extrapolation. A novel and simple approach, based on unsteady state mass balances, is presented herein for the simulation of the adsorption of Cr(III) ions from aqueous onto a low-cost adsorbent (leonardite). The proposed model overcomes the limitations of the commonly used analytical solution-based models without the need for complex mathematical methods. A set of experimental breakthrough curves obtained from lab-scale, fixed-bed columns was used to calibrate and validate the proposed model with a minimum number of parameters to be adjusted.

Recovery of ammonia from domestic wastewater effluents as liquid fertilizers by integration of natural zeolites and hollow fibre membrane contactors

The integration of up-concentration processes to increase the efficiency of primary sedimentation, as a solution to achieve energy neutral wastewater treatment plants, requires further post-treatment due to the missing ammonium removal stage. This study evaluated the use of zeolites as a post-treatment step, an alternative to the biological removal process. A natural granular clinoptilolite zeolite was evaluated as a sorbent media to remove low levels (up to 100mg-N/L) of ammonium from treated wastewater using batch and fixed bed columns. After being activated to the Na-form (Z-Na), the granular zeolite shown an ammonium exchange capacity of 29±0.8mgN-NH4+/g in single ammonium solutions and 23±0.8mgN-NH4+/g in treated wastewater simulating up-concentration effluent at pH=8. The equilibrium removal data were well described by the Langmuir isotherm. The ammonium adsorption into zeolites is a very fast process when compared with polymeric materials (zeolite particle diffusion coefficient around 3×10-12m2/s). Column experiments with solutions containing 100mgN-NH4+/L provide effective sorption and elution rates with concentration factors between 20 and 30 in consecutive operation cycles. The loaded zeolite was regenerated using 2g NaOH/L solution and the rich ammonium/ammonia concentrates 2-3g/L in NaOH were used in a liquid-liquid membrane contactor system in a closed-loop configuration with nitric and phosphoric acid as stripping solutions. The ammonia recovery ratio exceeded 98%. Ammonia nitrate and di-ammonium phosphate concentrated solutions reached up to 2-5% wt. of N.

Recovery of nutrients (N-P-K) from potassium-rich sludge anaerobic digestion side-streams by integration of a hybrid sorption-membrane ultrafiltration process: Use of powder reactive sorbents as nutrient carriers

Here, an alternative nutrient (N-P-K) recovery route from potassium-rich sludge anaerobic digestion side-streams using powder reactive sorbents (PRSs) is presented. In the first step, the optimum PRS system was determined in batch experiments with mixtures of: a) a sodium zeolite (NaP1) to facilitate the NH4+ and K+ sorption; b) a Ca-zeolite (CaP1) to facilitate the removal of P by formation of Ca-phosphates (e.g., CaHPO4(s)), and c) caustic magnesia containing mixtures of MgO to facilitate the formation of Mg/NH4/PO4 minerals (e.g., struvite and magnesium phosphates). Evaluation of the continuous and simultaneous N-P-K removal with mixtures of PRSs was carried out using a hybrid sorption/filtration system with ultrafiltration (UF) hollow-fibre membranes. The dosing ratios of the PRS mixtures were optimised on the basis of the equilibrium and kinetic sorption data, and a PRS dose (<2-5gPRS/L) was selected to ensure the hydraulic performance of the system. Under such conditions, and with synthetic anaerobic side-stream removal capacities (qt) of 220±10mgN-NH4/g, 35±5mgP-PO4/g, and 8±2mgK/g, removal efficiencies of 32±3, 78±5, and 26±3% for ammonium, phosphate, and potassium, respectively, were obtained for the binary mixtures of NaP1/CaP1 zeolites. Contrary to the batch results, the use of tertiary mixtures of NaP1/CaP1/MgO only improved the K removal capacity and efficiency to 18±2mgK/g and 55±4%, respectively, while the phosphate removal capacity and efficiency remained unchanged (ca. 35±3mgP-PO4/g; 80±5%) and the ammonium capacity and efficiency were reduced to 185±12mgN-NH4/g and 20±2%, respectively, due to the competing Mg2+ ion effect. Nutrient removal trials with real anaerobic side-streams using binary mixtures of Na/Ca zeolites showed a reduction of both the hydraulic performance and the nutrient removal ratios due to the presence of dissolved organic matter. However, constant removal ratios of N, P, and K were recorded throughout the filtration experiments. The loaded PRSs exhibited suitable nutrient release rates and bioavailability as co-substrates for soil quality improvement. Chemical analyses detected the formation of Ca/P/O and Mg/N/P/O neo-minerals; however, the mineralogical data revealed only the formation of struvite, even when no magnesium oxide was used.

Impacts on effluent contaminants from mine sites: risk assessment, fate, and distribution of pollution at basin scale

The environmental implications of mining activities are of worldwide concern. An environmental evaluation at the basin level was conducted because of widespread mining in Cajamarca in Northern Peru. A sediment monitoring program was developed at the Jequetepeque basin, located in Cajamarca. A total of 16 sites were monitored at three different times between June 2009 and July 2010, and a total of 42 samples were collected. All samples were analyzed by microwave digestion and by a sequential extraction scheme following the three-stage European Community Bureau of Reference (three-stage BCR) protocol. Trace element mobilization from the sediments to the water column was assessed by the risk assessment code (RAC). Spatial and temporal distribution of trace elements was evaluated by principal component analysis and hierarchical cluster analysis. Cd, Zn, As, and Pb showed the highest concentrations independent of season. Notably, Cu concentration and mobility increased during the wet season for all samples. Additionally, Hg concentration and mobility increased during the wet season near the mine sites. According to the enrichment factor, the highest enrichments of Cd, Zn, Pb, and As were related to mine runoff. The effect of trace elements near the mine sites at the Jequetepeque basin was considered a significant threat to the environment due to Cd, Zn, Pb, and As, and the concentrations of Cu and Hg were also considered a concern. This work establishes a baseline for the environmental quality status of the Jequetepeque basin that may support water quality management in Peru.

Wastewater treatment by MBR pilot plant: flat sheet and hollow fibre case studies

Abstract The design and implementation of membrane bioreactor (MBR) pilot plant was performed in order to treat municipal wastewater derived from the Suria municipality (Catalonia, Spain) wastewater treatment plant. Two submerged membrane configurations (flat sheet and hollow fibre) in MBR pilot plant were used for this purpose. The influent and effluents were monitored and controlled in order to ensure the achievements of the highest quality determined by Spanish legislation for water reuse. The Remosa company interest was focused in pilot plants applications for the small urban areas. Taking into account that the level of control and maintenance of this small plant can be lower than recommended, the start-up was performed under less favourable conditions without any sludge seed. After 8-months of continuous operation, the physico-chemical and microbial parameters of both MBR configurations achieved the water quality specifications defined for urban service, agricultural and recreational uses. The flat s...