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There is a growing interest in developing more environmentally friendly softeners for hardness reduction of water supplied for domestic consumption. This work focuses on exploring biopolymer-based softeners, through the surface modification of graphene oxide (GO) with the anionic biopolymer κ-carrageenan (GO-Si(κ)CRG). The performance of the modified GO to decrease the hardness of natural waters containing high levels of Ca2+ was assessed. The sorption efficiency was dependent on the initial Ca2+ concentration and on the sorbent dose, with 8–34% removal for GO and 21–100% for GO-Si(κ)CRG. The surface modification considerably improved the adsorptive efficiency and under certain experimental conditions, it was possible to convert very hard water (300 mg L−1 CaCO3) to soft water. Importantly, the performance was not affected by the presence of other ions typically found in natural bottled waters. The kinetics was well described by pseudo-first-order and diffusion models. The multi-linear nature observed in Boyd’s and Webber’s plots suggested that both film diffusion and pore diffusion controlled the sorption rate. The maximum Ca2+ sorption capacity at monolayer coverage of GO-Si(κ)CRG was 47.6 ± 3.2 mg g−1. The electrostatic attraction between sulfonate groups and calcium cations is likely to be the main mechanism involved in the sorption process of Ca2+ by GO-Si(κ)CRG. Overall, the results indicate good prospects for the development of a new class of softeners based on the GO modification described.

The main goal of this work was to produce an easily recoverable waste-based magnetic activated carbon (MAC) for an efficient removal of the antiepileptic pharmaceutical carbamazepine (CBZ) from wastewater. For this purpose, the synthesis procedure was optimized and a material (MAC4) providing immediate recuperation from solution, remarkable adsorptive performance and relevant properties (specific surface area of 551 m g and saturation magnetization of 39.84 emu g) was selected for further CBZ kinetic and equilibrium adsorption studies. MAC4 presented fast CBZ adsorption rates and short equilibrium times (< 30–45 min) in both ultrapure water and wastewater. Equilibrium studies showed that MAC4 attained maximum adsorption capacities (q) of 68 ± 4 mg g in ultrapure water and 60 ± 3 mg g in wastewater, suggesting no significant interference of the aqueous matrix in the adsorption process. Overall, this work provides evidence of potential application of a waste-based MAC in the tertiary treatment of wastewaters. [Figure not available: see fulltext.]., This work is a contribution to the project WasteMAC (POCI-01-0145-FEDER-028598) funded by FCT – Fundação para a Ciência e a Tecnologia, I.P., through national funds, and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. Thanks are also due for the financial support to CESAM (UID/AMB/50017/2019), to FCT/MCTES through national funds, and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. Marta Otero and Diogo Pereira thank FCT funding through IF Program (IF/00314/2015). Vânia Calisto is thankful to FCT for the Scientific Employment Stimulus support (CEECIND/00007/2017). María V. Gil acknowledges support from a Ramón y Cajal grant (RYC-2017-21937) of the Spanish government, co-financed by the European Social Fund (ESF).

Mercury and cadmium are considered by the water framework directive priority hazardous substances. In this work, the capacity of crab carapace and clam shell wastes to remove mercury and cadmium from water was evaluated under batch conditions, for realistic contamination scenarios in monometallic and binary solutions. The results evidenced that in monometallic solutions and under studied operational conditions, both biosorbents can achieve Hg2+ removal efficiencies higher than 80% and the kinetic process is well described by two of the most widely used equations, the pseudo-second order and the Elovich model. In terms of biosorption equilibrium, crab carapace and clam shell wastes displayed very distinct behaviours. While clam shells achieve the complete monolayer coverage and the isotherm is well described by the Langmuir model, crab carapace powder display a more unusual behaviour, that is well described by the BET isotherm, and is characterized by an almost convex shape to the concentration axis, with an infinite slope for an Hg2+ concentration in solution around 25 mu g/L. In binary solutions, both wastes are able to uptake simultaneously Hg2+ and Cd2+, however the uptake of Hg2+ was inhibited in some extent, attributed to the high kinetic and equilibrium selectivities of the bio-wastes for cadmium. (C) 2016 Elsevier Ltd. All rights reserved.

In view of a simple after-use separation, the potentiality of producing magnetic activated carbon (MAC) by intercalation of ferromagnetic metal oxide nanoparticles in the framework of a powder activated carbon (PAC) produced from primary paper sludge was explored in this work. The synthesis conditions to produce cost effective and efficient MACs for the adsorptive removal of pharmaceuticals (amoxicillin, carbamazepine, and diclofenac) from aqueous media were evaluated. For this purpose, a fractional factorial design (FFD) was applied to assess the effect of the most significant variables (Fe3+ to Fe2+ salts ratio, PAC to iron salts ratio, temperature, and pH), on the following responses concerning the resulting MACs: Specific surface area (SBET), saturation magnetization (Ms), and adsorption percentage of amoxicillin, carbamazepine, and diclofenac. The statistical analysis revealed that the PAC to iron salts mass ratio was the main factor affecting the considered responses. A quadratic linear regression model A = f(SBET, Ms) was adjusted to the FFD data, allowing to differentiate four of the eighteen MACs produced. These MACs were distinguished by being easily recovered from aqueous phase using a permanent magnet (Ms of 22&ndash, 27 emu g&minus, 1), and their high SBET (741&ndash, 795 m2 g&minus, 1) were responsible for individual adsorption percentages ranging between 61% and 84% using small MAC doses (35 mg L&minus, 1).

This work aimed at the microwave-assisted production of activated carbon (AC) from primary paper mill sludge (PS) for the adsorption of antibiotics from water. Production conditions, namely pyrolysis temperature, pyrolysis time and activating agent (KOH):PS ratio, were optimized as a function of product yield, specific surface area (SBET), total organic carbon (TOC) content and adsorptive removal percentage of two target antibiotics (amoxicillin (AMX) and sulfamethoxazole (SMX)). Under the optimized conditions (pyrolysis at 800 °C during 20 min and a KOH:PS ratio of 1:5), a microporous AC (MW800-20-1:5, with SBET = 1196 m2 g-1, TOC = 56.2% and removal of AMX and SMX = 85% and 72%, respectively) was produced and selected for further kinetic and equilibrium adsorption studies. The obtained results were properly described by the Elovich reaction-based kinetic model and the Langmuir equilibrium isotherm, with maximum adsorption capacities of 204 ± 5 mg g-1 and 217 ± 8 mg g-1 for AMX and SMX, respectively. Considering the satisfactory comparison of these results with the performance of commercial and alternative AC produced by conventional pyrolysis, this work demonstrated the feasibility of the microwave-assisted production of environmentally and energetically sustainable waste-based AC to be applied in the efficient removal of antibiotics from water., This work is a contribution to the project WasteMAC (POCI-01-0145-FEDER-028598) funded by FCT – Fundação para a Ciência e a Tecnologia, I.P., through national funds, and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. Thanks are also due for the financial support to CESAM (UIDB/50017/2020+UIDP/50017/2020), to FCT/MEC through national funds, and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. Marta Otero, Vânia Calisto and Guilaine Jaria are thankful to FCT for the Investigator Program (IF/00314/2015), the Scientific Employment Stimulus (CEECIND/00007/2017) and a PhD grant (SFRH/BD/138388/2018), respectively. María V. Gil acknowledges support from a Ramón y Cajal grant (RYC-2017-21937) of the Spanish government, co-financed by the European Social Fund (ESF).

The adsorption of pharmaceutical substances using carbonaceous materials, such as activated carbon (AC), biochar (BC) and hydrochar (HC), has received substantial attention by researchers working on water treatment, due to the simplicity, low-cost and high performance of this process. In order to widen the potentiality of these carbonaceous materials and to overcome some of their limitations, particularly the inefficient separation of powdered formulations from treated water, the incorporation of magnetic nanoparticles has been explored. The recovery of magnetic carbon materials (MCM) from the treated water can be attained by applying an external magnetic field, avoiding inefficient and costly filtration and centrifugation processes, typically applied in the case of non-magnetic carbonaceous adsorbents. In the last ten years, some work has been devoted to the preparation of MCM specifically from AC (MCACM), biochar (MCBCM) and hydrochar (MCHCM). This review aims to present the different aspects of using MCM in water treatment, namely in the removal of pharmaceutical compounds. The synthesis routes used to produce MCM, their physical, morphologic and chemical features, and their application in the removal of these micro-organic contaminants from water will be assessed. The advantages and disadvantages of using MCM in water treatment, and their comparative performance with the carbonaceous non-magnetic precursors will be also discussed in this review. published

Environmental contextStudying the mechanism of binding between metals and natural organic matter is fundamental to understanding the transport and availability of these contaminants in the environment. The influence of sample treatment on the purification of organic matter showed significant differences in the interaction with metals. The results will contribute to improved modelling of metal binding to organic matter in soils, thereby providing a basis for a more realistic risk assessment. AbstractWe studied the changes in metal binding characteristics of extracted humic acids induced by HF/HCl treatment followed by dialysis, i.e. the last step of the International Humic Substances Society (IHSS) extraction protocol. We performed metal binding experiments with both the alkaline-extracted material (AE) and the fully purified (FP) humic acid using the electrochemical stripping technique (AGNES) and modelled the results using the NICA-Donnan model. The results showed an increase of free Zn, Cd and Pb concentrations of similar to 1 order of magnitude for the AE compared with the FP. These differences may be mostly explained by the different carbon content (51.3% FP and 36.5% AE) associated with an AE/FP carboxyl ratio of 0.5. Simulations using the NICA-Donnan model showed that halving the amount of carboxylic groups (Q(max,1)) for the FP reduced this difference to 0.25 log units for Cd and Zn and to 0.15 log unit for Pb. There is a clear need for further research on the differences between purified v. less-disturbed natural organic material, which will contribute to improved modelling of metal binding to organic matter in soils, hence providing a basis for a more realistic risk assessment. Coordenadoria de Aperfeicoamento do Pessoal de Nivel Superior (CAPES CSF) [981313-6] Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq PVE) [400572/2013-3] French national research agency (ANR) [ANR-10-LABX-21-01/LABEX RESSOURCES 21] Portuguese national funding agency for science, research and technology [FCT-ANR/AAG-MAA/0065/2012] Region Lorraine

The efficiency of chitosan cross-linked with genipin (Chg) and cross-linked with genipin and grafted with caffeic acid (Ch(g+car)) to remove Hg(II) from waters was investigated. An optimal dose of 50 mg L-1 for both chitosan films was selected based on the equilibrium removal percentage and on the contact time required to attain the equilibrium. The sorption extent was dependent on the initial Hg(II) concentration (C-Hg,C-0), with removal efficiencies varying between 79% and 82% for C-Hg,C-0 = 0.05 mg L-1 and between 89% and 94% for C-Hg,C-0 = 0.50 mg L-1. Under ion competition, the Ch(g) and Ch(g+caf) films showed to be effective and selective for mercury in multimetallic solutions containing also cadmium and lead. In the case of natural river and seawaters, the mercury speciation played an important role in the overall sorption process, reducing the percentage removal of Hg. In terms of modeling, the kinetic data were well described by pseudo-first and pseudo-second order models, depending on the experimental conditions. The diffusion models suggested that the entire sorption process of Hg(II) by both Chg and Chg+caf films was essentially controlled by pore diffusion. The equilibrium data were well described by the Sips isotherm, and the estimated capacity was 2.2 and 4.0 mg g(-1) for Chg and Ch(g+caf) films, respectively. In the whole, the results showed that the sorption efficiency was improved by grafting caffeic acid to the polymeric chains of chitosan cross-linked with genipin. (C) 2016 Elsevier B.V. All rights reserved.

We report on an international proficiency test (PT) scheme for mercury (Hg) determination in soil, sediment, fish and human-hair samples (ILAE-Hg-02). For total-Hg determination, 74% of participants had a satisfactory performance (|z-score| ≤ 2), 8% had a questionable performance and 18% required action (|z-score| > 3). The best results were obtained for soil, while fish yielded the most-biased results, reflecting the analytical problems of quantifying Hg at low concentrations. Proficiency in the extraction of organometallic and available metal fractions was an important goal of the ILAE-Hg-02 and it was concluded that most laboratories are still not acquainted with the procedures for Hg fractionation; we therefore discuss their importance and highlight the need for more PT schemes dedicated to this matter, as they are an important tools in the standardization of procedures and for the development of adequate quality control/quality analysis protocols and certified reference materials.

The technical feasibility of using stopper-derived cork as an effective biosorbent towards bivalent mercury at environmentally relevant concentrations and conditions was evaluated in this study. Only 25 mg/L of cork powder was able to achieve 94 % of mercury removal for an initial mercury concentration of 500 mu g/L. It was found that under the conditions tested, the efficiency of mercury removal expressed as equilibrium removal percentage does not depend on the amount of cork or its particle size, but is very sensitive to initial metal concentration, with higher removal efficiencies at higher initial concentrations. Ion exchange was identified as one of the mechanisms involved in the sorption of Hg onto cork in the absence of ionic competition. Under ionic competition, stopper-derived cork showed to be extremely effective and selective for mercury in binary mixtures, while in complex matrices like seawater, moderate inhibition of the sorption process was observed, attributed to a change in mercury speciation. The loadings achieved are similar to the majority of literature values found for other biosorbents and for other metals, suggesting that cork stoppers can be recycled as an effective biosorbent for water treatment. However, the most interesting result is that equilibrium data show a very rare behaviour, with the isotherm presenting an almost square convex shape to the concentration axis, with an infinite slope for an Hg concentration in solution around 25 mu g/L.

A microporous material denoted ETS-4 was used as the decontaminant agent to treat water with a low level of Hg contamination. The effectiveness of the treatment was evaluated by assessment of the efficiency of Hg removal and ecotoxicological responses. The results showed that under highly competitive conditions the removal of Hg ranged between 58 % and 73 % depending upon the initial Hg concentration, and that Hg removal was reflected in decreased toxicity to some organisms. The ecotoxicological data indicated that the bacterium Vibrio fischeri was the least sensitive organism tested, as no toxicity was observed in either pre- or post-treatment waters. Daphnia magna was highly sensitive to Hg. Mercury removal by ETS-4 was not sufficient to completely remove the toxicity of Hg to D. magna. However, it was effective in the complete reduction of toxicity for the green alga, Pseudokirchneriella subcapitata.

In the present work, the applicability of thin mercury film on a rotating disk electrode (TMF-RDE), to assess the free metal ion concentration by the absence of gradients and Nernstian equilibrium stripping (AGNES), is evaluated. The thickness of the mercury film and several AGNES parameters has been optimized. A nominal 16 nm film is chosen due to the higher signal (faradaic current) relative to the value of the noise (capacitive current). Due to the smaller volume to area ratio, the deposition time needed to reach a certain preconcentration factor ( Y ) is much shorter than in larger electrodes, like the HMDE. The limit of detection (3 σ ) for lead(II) is 7.4 × 10 −9 M and 7.2 × 10 −8 M for a Y of 5000 (deposition time of 150 s) and 1000 (deposition time of 100 s), respectively. A specific mathematical treatment is developed in order to subtract a corrected blank taking into account the degradation of the thin film (presumably, falling down of drops). The couple TMF-RDE/AGNES is successfully applied for speciation purposes in the systems Pb(II)–latex nanospheres and Pb(II)–IDA (iminodiacetic acid), where the stability constants calculated for both systems agree with values reported in the literature.