Cidália M.S. Botelho

Arsenic and antimony in water and wastewater: Overview of removal techniques with special reference to latest advances in adsorption

Arsenic and antimony are metalloids, naturally present in the environment but also introduced by human activities. Both elements are toxic and carcinogenic, and their removal from water is of unquestionable importance. The present article begins with an overview of As and Sb chemistry, distribution and toxicity, which are relevant aspects to understand and develop remediation techniques. A brief review of the recent results in analytical methods for speciation and quantification was also provided. The most common As and Sb removal techniques (coagulation/flocculation, oxidation, membrane processes, electrochemical methods and phyto and bioremediation) are presented with discussion of their advantages, drawbacks and the main recent achievements. Literature review on adsorption and biosorption were focused in detail. Considering especially the case of developing countries or rural communities, but also the finite energy resources that over the world are still dependent, recent research have focused especially readily available low-cost adsorbents, as minerals, wastes and biosorbents. Many of these alternative sorbents have been presenting promising results and can be even superior when compared to the commercial ones. Sorption capacities were accurately compiled for As(III,V) and Sb(III,V) species in order to provide to the reader an easy but detailed comparison. Some aspects related to experimental conditions, comparison criteria, lack of research studies, economic aspects and adsorption mechanisms were critically discussed.

A review of the use of red mud as adsorbent for the removal of toxic pollutants from water and wastewater

Red mud (an aluminium industry waste) has received wide attention as an effective adsorbent for water pollution control, showing significant adsorption potential for the removal of various aquatic pollutants. In this review, an extensive list of red‐mud‐based adsorbents has been compiled and their adsorption capacities (maximum uptake value of the adsorbent for the pollutant or adsorbate being removed) for various aquatic pollutants (metal ions, dyes, phenolic compounds, inorganic anions) are presented. The review provides a summary of recent information obtained using batch studies and deals with the adsorption mechanisms involved. It is evident from the literature survey that red mud has been found to be efficient for the removal of various aquatic pollutants, especially arsenic and phosphate. However, there is still a need to investigate the practical utility of these adsorbents on a commercial scale.

Coconut-based biosorbents for water treatment — A review of the recent literature

Biosorption is an emerging technique for water treatment utilizing abundantly available biomaterials (especially agricultural wastes). Among several agricultural wastes studied as biosorbents for water treatment, coconut has been of great importance as various parts of this tree (e.g. coir, shell, etc.) have been extensively studied as biosorbents for the removal of diverse type of pollutants from water. Coconut-based agricultural wastes have gained wide attention as effective biosorbents due to low-cost and significant adsorption potential for the removal of various aquatic pollutants. In this review, an extensive list of coconut-based biosorbents from vast literature has been compiled and their adsorption capacities for various aquatic pollutants as available in the literature are presented. Available abundantly, high biosorption capacity, cost-effectiveness and renewability are the important factors making these materials as economical alternatives for water treatment and waste remediation. This paper presents a state of the art review of coconut-based biosorbents used for water pollution control, highlighting and discussing key advancement on the preparation of novel adsorbents utilizing coconut wastes, its major challenges together with the future prospective. It is evident from the literature survey that coconut-based biosorbents have shown good potential for the removal of various aquatic pollutants. However, still there is a need to find out the practical utility of such developed adsorbents on commercial scale, leading to the superior improvement of pollution control and environmental preservation.

Selenium contaminated waters: An overview of analytical methods, treatment options and recent advances in sorption methods

Selenium is an essential trace element for many organisms, including humans, but it is bioaccumulative and toxic at higher than homeostatic levels. Both selenium deficiency and toxicity are problems around the world. Mines, coal-fired power plants, oil refineries and agriculture are important examples of anthropogenic sources, generating contaminated waters and wastewaters. For reasons of human health and ecotoxicity, selenium concentration has to be controlled in drinking-water and in wastewater, as it is a potential pollutant of water bodies. This review article provides firstly a general overview about selenium distribution, sources, chemistry, toxicity and environmental impact. Analytical techniques used for Se determination and speciation and water and wastewater treatment options are reviewed. In particular, published works on adsorption as a treatment method for Se removal from aqueous solutions are critically analyzed. Recent published literature has given particular attention to the development and search for effective adsorbents, including low-cost alternative materials. Published works mostly consist in exploratory findings and laboratory-scale experiments. Binary metal oxides and LDHs (layered double hydroxides) have presented excellent adsorption capacities for selenium species. Unconventional sorbents (algae, agricultural wastes and other biomaterials), in raw or modified forms, have also led to very interesting results with the advantage of their availability and low-cost. Some directions to be considered in future works are also suggested.

Use of cork powder and granules for the adsorption of pollutants: A review

Cork powder and granules are the major subproducts of the cork industry, one of the leading economic activities in Portugal and other Mediterranean countries. Many applications have been envisaged for this product, from cork stoppers passing through the incorporation in agglomerates and briquettes to the use as an adsorbent in the treatment of gaseous emissions, waters and wastewaters. This paper aims at reviewing the state of the art on the properties of cork and cork powder and their application in adsorption technologies. Cork biomass has been used on its original form as biosorbent for heavy metals and oils, and is also a precursor of activated carbons for the removal of emerging organic pollutants in water and VOCs in the gas phase. Through this literature review, different potential lines of research not yet explored can be more easily identified.

Copper removal by algal biomass : Biosorbents characterization and equilibrium modelling

The general principles of Cu(II) binding to algal waste from agar extraction, composite material and algae Gelidium, and different modelling approaches, are discussed. FTIR analyses provided a detailed description of the possible binding groups present in the biosorbents, as carboxylic groups (D-glucuronic and pyruvic acids), hydroxyl groups (cellulose, agar and floridean starch) and sulfonate groups (sulphated galactans). Potentiometric acid-base titrations showed a heterogeneous distribution of two major binding groups, carboxyl and hydroxyl, following the quasi-Gaussian affinity constant distribution suggested by Sips, which permitted to estimate the maximum amount of acid functional groups (0.36, 0.25 and 0.1 mmol g(-1)) and proton binding parameters (pK(H)=5.0, 5.3 and 4.4; m(H)=0.43, 0.37, 0.33), respectively for algae Gelidium, algal waste and composite material. A non-ideal, semi-empirical, thermodynamically consistent (NICCA) isotherm fitted better the experimental ion binding data for different pH values and copper concentrations, considering only the acid functional groups, than the discrete model. Values of pK(M) (3.2; 3.6 and 3.3), n(M) (0.98, 0.91, 1.0) and p (0.67, 0.53 and 0.43) were obtained, respectively for algae Gelidium, algal waste and composite material. NICCA model reflects the complex macromolecular systems that take part in biosorption considering the heterogeneity of the biosorbent, the competition between protons and metals ions to the binding sites and the stoichiometry for different ions.

Application of the Nernst–Planck approach to lead ion exchange in Ca-loaded Pelvetia canaliculata

Ca-loaded Pelvetia canaliculata biomass was used to remove Pb(2+) in aqueous solution from batch and continuous systems. The physicochemical characterization of algae Pelvetia particles by potentiometric titration and FTIR analysis has shown a gel structure with two major binding groups - carboxylic (2.8 mmol g(-1)) and hydroxyl (0.8 mmol g(-1)), with an affinity constant distribution for hydrogen ions well described by a Quasi-Gaussian distribution. Equilibrium adsorption (pH 3 and 5) and desorption (eluents: HNO(3) and CaCl(2)) experiments were performed, showing that the biosorption mechanism was attributed to ion exchange among calcium, lead and hydrogen ions with stoichiometry 1:1 (Ca:Pb) and 1:2 (Ca:H and Pb:H). The uptake capacity of lead ions decreased with pH, suggesting that there is a competition between H(+) and Pb(2+) for the same binding sites. A mass action law for the ternary mixture was able to predict the equilibrium data, with the selectivity constants alpha(Ca)(H)=9+/-1 and alpha(Ca)(Pb)=44+/-5, revealing a higher affinity of the biomass towards lead ions. Adsorption (initial solution pH 4.5 and 2.5) and desorption (0.3M HNO(3)) kinetics were performed in batch and continuous systems. A mass transfer model using the Nernst-Planck approximation for the ionic flux of each counter-ion was used for the prediction of the ions profiles in batch systems and packed bed columns. The intraparticle effective diffusion constants were determined as 3.73x10(-7)cm(2)s(-1) for H(+), 7.56x10(-8)cm(2)s(-1) for Pb(2+) and 6.37x10(-8)cm(2)s(-1) for Ca(2+).

Watershed model parameter estimation and uncertainty in data-limited environments

Parameter uncertainty and sensitivity for a watershed-scale simulation model in Portugal were explored to identify the most critical model parameters in terms of model calibration and prediction. The research is intended to help provide guidance regarding allocation of limited data collection and model parameterization resources for modelers working in any data and resource limited environment. The watershed-scale hydrology and water quality simulation model, Hydrologic Simulation Program - FORTRAN (HSPF), was used to predict the hydrology of Lis River basin in Portugal. The model was calibrated for a 5-year period 1985-1989 and validated for a 4-year period 2003-2006. Agreement between simulated and observed streamflow data was satisfactory considering the performance measures such as Nash-Sutcliffe efficiency (E), deviation runoff (Dv) and coefficient of determination (R2). The Generalized Likelihood Uncertainty Estimation (GLUE) method was used to establish uncertainty bounds for the simulated flow using the Nash-Sutcliffe coefficient as a performance likelihood measure. Sensitivity analysis results indicate that runoff estimations are most sensitive to parameters related to climate conditions, soil and land use. These results state that even though climate conditions are generally most significant in water balance modeling, attention should also focus on land use characteristics as well. Specifically with respect to HSPF, the two most sensitive parameters, INFILT and LZSN, are both directly dependent on soil and land use characteristics. HSPF calibration/validation study on data limited watersheds.HSPF water balance parameters sensitivity analysis reported similar results for different watershed studies.The effect of model uncertainty is determined by the threshold value established to obtain the confidence interval.Accuracy of climate and land use data is very important for model performance.

Surface Water Quality Assessment of Lis River Using Multivariate Statistical Methods

This study presents the application of multivariate statistical tools for the evaluation of spatial variations and the interpretation of water quality data obtained in a monitoring program of Lis river basin surface water, Portugal. Twenty-seven physicochemical and microbiological parameters were determined in six water sampling campaigns at 16 monitoring sites during the period from September 2003 to November 2006. Correlation analysis, principal component analysis, and cluster analysis were performed to evaluate the main water pollution sources and to characterize the spatial distribution of water pollution profiles in river basin. The results achieved with the statistical methodologies led to distinguish natural and anthropogenic pollution sources. Additionally, monitoring sites with similar water pollution profile were identified, indicating that some monitoring locations can be changed to improve the spatial characterization of water quality in the river basin. CBO, CQO, P, and N were identified as significant variables affecting spatial variations, namely in the Lis river middle reach. Besides the identification of main pollution sources, the applied statistical tools were able to identify spatial patterns of water pollution in Lis river basin, which further helps in the reassessment of the number and location of monitoring sites.

Interactions of lead(II) with natural river water: part I. Soluble organics

Abstract A comparative study of dissolved complexants for lead( II ) on three different sites along a polluted river was undertaken. Intrinsic and apparent acidity constants were obtained from potentiometric titrations. The difference between the two values in all samples reflects conformational and electrostatic effects during titrations. Complexometric capacities for Pb( II ) were estimated and average equilibrium constants were obtained from DPASV voltammetric titration curves. Differential equilibrium functions were defined. At the pH measured in the river, the affinity of metal ions for ligands decreases with increasing metal loading of solutions, due to the heterogeneous effect of the ligands.