Sílvia C.R. Santos

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.

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.

Treatment of a simulated textile wastewater in a sequencing batch reactor (SBR) with addition of a low-cost adsorbent

Color removal from textile wastewaters, at a low-cost and consistent technology, is even today a challenge. Simultaneous biological treatment and adsorption is a known alternative to the treatment of wastewaters containing biodegradable and non-biodegradable contaminants. The present work aims at evaluating the treatability of a simulated textile wastewater by simultaneously combining biological treatment and adsorption in a SBR (sequencing batch reactor), but using a low-cost adsorbent, instead of a commercial one. The selected adsorbent was a metal hydroxide sludge (WS) from an electroplating industry. Direct Blue 85 dye (DB) was used in the preparation of the synthetic wastewater. Firstly, adsorption kinetics and equilibrium were studied, in respect to many factors (temperature, pH, WS dosage and presence of salts and dyeing auxiliary chemicals in the aqueous media). At 25 °C and pH 4, 7 and 10, maximum DB adsorption capacities in aqueous solution were 600, 339 and 98.7 mg/g, respectively. These values are quite considerable, compared to other reported in literature, but proved to be significantly reduced by the presence of dyeing auxiliary chemicals in the wastewater. The simulated textile wastewater treatment in SBR led to BOD5 removals of 53-79%, but color removal was rather limited (10-18%). The performance was significantly enhanced by the addition of WS, with BOD5 removals above 91% and average color removals of 60-69%.

Arsenate and arsenite adsorption onto iron-coated cork granulates

There is a growing demand for low-cost, effective adsorbents for arsenic removal from water intended for human consumption in affected rural areas. This work presents a novel adsorbent based on the coating of cork granulates with iron (oxy)hydroxides for the removal of As(III) and As(V) from aqueous matrices. A 26-3 fractional factorial design was used to determine the optimal conditions for the iron coating procedure. The optimal adsorbent was produced by coating low-density cork granulates with iron (oxy)hydroxides precipitated from a 0.05 mol L-1 FeCl3 solution at pH 7, 20 °C temperature and 20 g L-1 S/L ratio, in a single coating cycle. Arsenic adsorption was found to be dependent on pH, with inverse trends for As(III) and As(V). The iron leaching from the adsorbent was also taken into account to select the optimum pH, which was pH 9 for As(III) and pH 3 for As(V). Adsorption kinetics were better described by the pseudo-second-order model for As(III) and the Elovich model for As(V). Equilibrium was reached in 16 h for As(III) at pH 9 and 48 h for As(V) at pH 3. The isotherm models indicated different adsorption behaviours for As(III) and As(V), with better fits by Langmuir and Freundlich models, respectively. The Langmuir maximum adsorption capacity of iron-coated cork adsorbent for As(III) at pH 9 was 4.9 ± 0.3 mg g-1. However, at low equilibrium concentrations, As(V) adsorption was higher than As(III) (e.g. 2.1 ± 0.2 mg g-1 in equilibrium with 0.16 ± 0.03 mg L-1). Speciation studies and XPS analyses indicated that no substantial oxidation of As(III) to As(V) occurred during the adsorption process. The study shows that iron coating can enhance both arsenate and arsenite adsorption capacity of cork materials, leading to an innovative natural adsorbent with high resilience and stability, with possible application in arsenic remediation.

Macroalgae Biomass as Sorbent for Metal Ions

Abstract Seaweeds play a key role in the aquatic environment, but over the last years algal blooms have increased on maritime coasts, fouling beaches and threatening tourism. Biosorption has captured scientific interest in the last decades as a possible way to manage biowaste and to develop a cost-effective technology to detoxificate heavy metal–bearing waters and recover the metals. Algae, in their native or modified forms, especially from the brown division, have proven to be good sequestrants for different cationic heavy metals (Pb, Zn, Cr(III), Ni, Cd), although they are not as effective for anionic species such as arsenic and antimony. The present chapter presents the state-of-the-art of the potential use of dead marine macroalgae as a low-cost biosorbent for removal of heavy metals and metalloids from water. Physical and chemical characterization of the algae are reviewed; biosorption mechanisms summarized and the biosorption capacities of some brown, green, and red algae analyzed; studies in continuous mode and using industrial effluents are also covered. The chapter also describes pretreatments reported in literature that can be applied to the seaweeds to enhance their biosorption ability and properties, namely, protonation, saturation with cations, aldehyde treatment, oxidation, encapsulation, and the use of algal waste.