Oriol Gibert

The most common reactive material used for the construction of a permeable reactive barrier (PRB) is zero valent iron (ZVI), however, its processing can generate corrosive effects that reduce the efficiency of the barrier. The present study makes a major contribution to understanding new reactive materials as natural and synthetic, easy to obtain, economical and environmentally friendly as possible substitutes for the traditional ZHV to be used as filters in the removal of three transition metals (Zn, Cu, Cd). To assess the ability to remove these pollutants, a series of batch and column tests were carried out at laboratory scale with these materials. Through BACH tests, four of seven substances with a removal percentage higher than 99% were prioritized (cabuya, natural clinoptilolite zeolites, sodium mordenite and mordenite). From this group of substances, column tests were performed where it is evidenced that cabuya fiber presents the lowest absorption time (≈189 h) while natural zeolite mordenite shows the highest time (≈833 h). The latter being the best option for the PRB design. The experimental values were also reproduced by the RETRASO code; through this program, the trend between the observed and simulated values with respect to the best reactive substance was corroborated.

An approach for the remediation of heavy metal-contaminated wastewater that is gaining increasing attention is the application of hydroxyapatite (HAP)-based particles. HAP is conventionally synthesized through wet chemical precipitation of calcium and phosphate ions, although later studies have focused on HAP synthesis from solid calcite contacted with a phosphate solution under ambient conditions. This synthesis route can allow saving soluble Ca-chemicals and, thus, make the process more cost-efficient. The aim of this study was to coat natural calcite powder with a layer of HAP for the removal of Zn and Cu from contaminated water. For this purpose, a HAP layer was synthesized on calcite particles, characterized using several complementary techniques and evaluated for the removal of Zn and Cu from synthetic solutions. Sorption kinetics and equilibrium isotherms, as well as the effect of sonication of the synthesized sample on its sorption performance, were determined. The results showed that calcite particles were efficiently coated with a HAP layer with high capacity in removing Zn and Cu from acidic solutions, with a q_max of 34.97 mg/g for Zn (increased to 37.88 g/mg after sonication of the sample) and 60.24 mg/g for Cu (which hardly varied with sonication). The mechanisms behind the sorption of Zn and Cu onto HAP, inferred from pH changes, the relation between metal uptake and Ca²⁺ release and XRD analysis, included surface complexation, ion exchange and precipitation of new Zn- and Cu-containing phases.

The primary problem for the application of microfiltration (MF) and ultrafiltration (UF) membrane technology is membrane fouling. Such is the case that understanding membrane fouling has become one of the major factors driving MF and UF membrane technology forward. Nevertheless, identifying the constituents that most contribute to membrane fouling and quantifying how they are detached when backwashing (BW) and cleaning-in-place (CIP) are applied still remains a challenging task. The aim of the present study was to quantify membrane fouling development during filtration and membrane fouling detachment during BW and CIP in terms of membrane permeability changes and masses of inorganic and organic constituents accumulated on the membrane. The study was conducted using bench-scale MF and UF modules fed with coagulated and settled water coming from a drinking water treatment plant and operated under dead-end and cross-flow operation modes. The experiments consisted inconsecutive permeation (20 min) alternated with BW with permeate water (1.0 min) (periodically chemically assisted with NaClO and NaOH) and followed by a two-stage CIP consisting first in an oxidising and basic step (NaClO and NaOH) and second in an acidic step (citric acid). Feed, permeate, retentate (when present) and cleaning discharge streams were monitored for turbidity, total and dissolved organic carbon (TOC and DOC, respectively), UV₂₅₄ and inorganic ions (Al, Fe, P). DOC was fractionated by high-performance size exclusion chromatography to gain insight into the behaviour of the different organic fractions. Results showed that both MF and UF membranes successfully removed turbidity, Al and Fe, whereas UV₂₅₄ was moderately removed and TOC and DOC poorly removed, with removal percentages higher for UF than for MF. With regard to the organic fractions, the largest molecular weight compounds were moderately removed while the smallest organic fractions seemed to totally permeate through both membranes. The results also showed that foulants were poorly washed out from the membrane by BW, but better extracted by the two-stage CIP up to a complete detachment for some foulants.

Membrane fouling is an inherent phenomenon in ultrafiltration (UF) membrane processes, making it necessary to periodically perform backwashes (BW) and chemical “cleanings in place” (CIP) to restore the initial permeability of the membrane. The objective of this study was (1) to explore systematically the effect of distinct BW-related variables (BW transmembrane pressure, duration, frequency and composition) on the reversibility of UF membrane fouling and on the permeate quality (in terms of total organic carbon, turbidity and UV absorbance) over successive filtration/BW cycles; and (2) to identify which organic fractions were most removed by the membrane and, of these, which were most detached after BW, alkaline and oxidant CIP and acid CIP episodes. For this purpose, a bench-scale outside-in hollow fibre module operated under dead-end filtration mode at constant transmembrane pressure and treating settled water from a drinking water treatment plant was employed. Dissolved organic carbon fractionation was performed by high-performance size-exclusion chromatography. Results showed that, in general, the more intensive the BW was (in terms of high transmembrane pressure, shortened frequency and prolonged duration) the more effective it was in removing fouling from the membrane. Concerning the composition of the water used for the BW, the addition of NaClO led to maximum fouling reversibility, closely followed by the combination of NaOH + NaClO, while citric acid and NaOH contributed little compared to water alone. However, results also showed that irreversible fouling was never completely avoided whatever the BW regime applied, leading to a gradual increase in the total resistance over time. Larger differences in the behaviour of the different organic fractions were observed. UF membrane preferentially retained the heaviest fraction of biopolymers (BP), while the intermediate fraction of humic substances (HS) was removed at a lower percentage and the lighter fractions seemed to entirely pass through the UF membrane. The successive application of BW and CIPs resulted in the detachment from the membrane of a significant percentage of the retained BP, whereas only a modest percentage of the retained HS.

Nanofiltration (NF) membranes can be used in different configurations. The aim of this work was to determine the reliability of the data obtained using flat-sheet (FS) laboratory-scale configuration when NF membranes are implemented at industrial scale level using spiral wound (SW) configuration. Ion rejections in salt mixtures with the two configurations types were analysed, modelled, evaluated and compared. In both cases of the study, the operation was carried out in cross-flow mode and with recirculation of permeate and concentrate streams into the feed tank. Different feed synthetic salt solutions were used based on a dominant and a trace salt. In both cases, the operating temperature was kept constant (21.5 ± 2.5°C), and the trans-membrane pressure range varied from the osmotic pressure to 20 bar. The same NF membrane was used for both configurations: NF270 (Dow Chemical). The solution–diffusion–electromigration–film model was employed to describe the experimental results. Comparing both membrane configurations, the trans-membrane flux obtained with the FS configuration was higher than that observed with the SW configuration under the same operating conditions. In general, it is proved that ion rejection curves for both membrane configurations were fairly similar. Moreover, the membrane permeances with respect to each ion in both configurations were quantitatively similar.

A permeable reactive barrier (PRB) was installed in Aznalcóllar (Spain) in order to rehabilitate the Agrio aquifer groundwater severely contaminated with acid mine drainage after a serious mining accident. The filling material of the PRB consisted of a mixture of calcite, vegetal compost and, locally, Fe⁰ and sewage sludge. Among the successes of the PRB are the continuous neutralisation of pH and the removal of metals from groundwater within the PRB (removals of >95 %). Among the shortcomings are the improper PRB design due to the complexity of the internal structure of the Agrio alluvial deposits (which resulted in an inefficient capture of the contaminated plume), the poor degradability of the compost used and the short residence time within the PRB (which hindered a complete sulphate reduction), the clogging of a section of the PRB and the heterogeneities of the filling material (which resulted in preferential flows within the PRB). Undoubtedly, it is only through accumulated experience at field-scale systems that the potentials and limits of the PRB technology can be determined.