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The wide occurrence of pharmaceuticals in aquatic environments urges the development of cost-effective solutions for their removal from water. In a circular economy context, primary paper mill sludge (PS) was used to produce activated carbon (AC) aiming the adsorptive removal of these contaminants. The use of low-cost precursors for the preparation of ACs capable of competing with commercial ACs continues to be a challenge. A full factorial design of four factors (pyrolysis temperature, residence time, precursor/activating agent ratio, and type of activating agent) at two levels was applied to the production of AC using PS as precursor. The responses analysed were the yield of production, percentage of adsorption for three pharmaceuticals (sulfamethoxazole, carbamazepine, and paroxetine), specific surface area (S BET ), and total organic carbon (TOC). Statistical analysis was performed to evaluate influencing factors in the responses and to determine the most favourable production conditions. Four ACs presented very good responses, namely on the adsorption of the pharmaceuticals under study (average adsorption percentage around 78%, which is above that of commercial AC), and S BET between 1389 and 1627 m 2  g -1 . A desirability analysis pointed out 800 °C for 60 min and a precursor/KOH ratio of 1:1 (w/w) as the optimal production conditions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A waste-based alternative activated carbon (AAC) was produced from paper mill sludge under optimized conditions. Aiming its application in tertiary wastewater treatment, AAC was used for the removal of carbamazepine, sulfamethoxazole, and paroxetine from biologically treated municipal wastewater. Kinetic and equilibrium adsorption experiments were run under batch operation conditions. For comparison purposes, they were also performed in ultrapure water and using a high-performance commercial AC (CAC). Adsorption kinetics was fast for the three pharmaceuticals and similar onto AAC and CAC in either wastewater or ultrapure water. However, matrix effects were observed in the equilibrium results, being more remarkable for AAC. These effects were evidenced by Langmuir maximum adsorption capacities (q m , mg g -1 ): for AAC, the lowest and highest q m were 194 ± 10 (SMX) and 287 ± 9 (PAR), in ultrapure water, and 47 ± 1 (SMX) and 407 ± 14 (PAR), in wastewater, while for CAC, the lowest and highest q m were 118 ± 7 (SMX) and 190 ± 16 (PAR) in ultrapure water and 123 ± 5 (SMX) and 160 ± 7 (CBZ) in wastewater. It was found that the matrix pH played a key role in these differences by controlling the surface electrostatic interactions between pharmaceutical and AC. Overall, it was evidenced the need of adsorption results in real matrices and demonstrated that AAC is a promising option to be implemented in tertiary wastewater treatments for pharmaceuticals' removal. Graphical abstract Production of an alternative activated carbon (AC) comparing favourably with a commercial AC in the removal of neutral and positive pharmaceuticals from wastewater.

In this work, a granular activated carbon (GAC) was produced using primary paper mill sludge (PS) as raw material and ammonium lignosulfonate (AL) as binder agent. PS is a residue from the pulp and paper industry and AL is a by-product of the cellulose pulp manufacture and the proposed production scheme contributes for their valorisation together with important savings in GAC precursors. The produced GAC (named PSA-PA) and a commercially available GAC (GACN), used as reference material, were physically and chemically characterized. Then, these materials were tested in batch experiments for the adsorption of carbamazepine (CBZ), sulfamethoxazole (SMX), and paroxetine (PAR) from ultra-pure water and wastewater. Even though GACN and PSA-PA possess very similar specific surface areas (S BET ) (629 and 671 m 2  g -1 , respectively), PSA-PA displayed lower maximum adsorption capacities (q m ) than GACN for the pharmaceuticals here studied (6 ± 1-44 ± 5 mg g -1 and 49 ± 6-106 ± 40 mg g -1 , respectively). This may be related to the comparatively higher incidence of mesopores in GACN, which might have positively influenced its adsorptive performance. Moreover, the highest hydrophobic character and degree of aromaticity of GACN could also have contributed to its adsorption capacity. On the other hand, the performance of both GACs was significantly affected by the matrix in the case of CBZ and SMX, with lower q m in wastewater than in ultra-pure water. However, the adsorption of PAR was not affected by the matrix. Electrostatic interactions and pH effects might also have influenced the adsorption of the pharmaceutical compounds in wastewater., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Pulp and paper industry produces massive amounts of sludge from wastewater treatment, which constitute an enormous environmental challenge. A possible management option is the conversion of sludge into carbon-based adsorbents to be applied in water remediation. For such utilization it is important to investigate if sludge is a consistent raw material originating reproducible final materials (either over time or from different manufacturing processes), which is the main goal of this work. For that purpose, different primary (PS) and biological sludge (BS) batches from two factories with different operation modes were sampled and subjected to pyrolysis (P materials) and to pyrolysis followed by acid washing (PW materials). All the materials were characterized by proximate analysis, total organic carbon (TOC) and inorganic carbon (IC), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and N 2 adsorption isotherms (specific surface area (S BET )and porosity determination). Sludge from the two factories proved to have distinct physicochemical properties, mainly in what concerns IC. After pyrolysis, the washing step was essential to reduce IC and to considerably increase S BET , yet with high impact in the final production yield. Among the materials here produced, PW materials from PS were those having the highest S BET values (387-488 m 2  g -1 ). Overall, it was found that precursors from different factories might originate final materials with distinct characteristics, being essential to take into account this source of variability when considering paper mill sludge as a raw material. Nevertheless, for PS, low variability was found between batches, which points out to the reliability of such residues to be used as precursors of carbon adsorbents., (Copyright © 2016 Elsevier Ltd. All rights reserved.)