Use of waste marble powder for the synthesis of novel calcium-rich biochar: Characterization and application for phosphorus recovery in continuous stirring tank reactors.

This study investigates-for the first time-the synthesis of a novel Ca-rich biochar (N-Ca-B) and its potential use for phosphorus (P) recovery from both synthetic solutions (SS) and treated urban wastewater (TUW) in a continuous stirring tank reactor (CSTR) mode. The novel biochar was synthesized by pyrolysis at 900 °C of a mixture composed of three different materials: animal biomass (poultry manure; PM), lignocellulosic waste (date palm fronds; DPFs), and abundant mineral waste (waste marble powder; WMP). Characterization of N-Ca-B showed that it has good textural properties: well-developed porosity, and high specific surface area. Furthermore, high calcium hydroxide (Ca(OH)2) and calcium oxides (CaO) nanoparticle loads were observed on the biochar surface. The dynamic CSTR assays indicated that the P recovery efficiency mainly depended on the biochar mass, P influent concentration, and, especially, the Ca content of the feeding solution. Owing to its richness in Ca cations, TUW exhibited the highest adsorbed P amount (109.2 mg g-1), i.e., about 14% larger than the SS. P recovery occurs through precipitation as hydroxyapatite, surface complexation, and electrostatic interactions with positively charged biochar particles. In real-world scenarios, CSTR systems can be applied as a tertiary treatment step in existing wastewater treatment plants (WWTPs). Decanted P-loaded biochar can be used in agriculture as a slow-release fertilizer instead of commercial products.

Facile synthesis of double-cross-linked alginate-based hydrogel: Characterization and use in a context of circular economy for cationic dye removal.

Hydrogels based on natural polysaccharides have received special attention in the last decade due to their interesting features, such as availability, biocompatibility, biodegradability and safety. Such characteristics may make them sustainable and eco-friendly materials for water and wastewater treatment, meeting the concept of circular economy. In this study, a novel double-cross-linked alginate-based hydrogel has been successfully synthesized using epichlorhydrin and sodium trimetaphosphate (STMP) as cross-linker agents and then used for the removal of methylene blue (MB) dye under different operating conditions. The obtained hydrogel was deeply characterized by using various analytical techniques, namely Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and differential scanning calorimetry. Experimental results showed that the synthesized double cross-linked hydrogel with relatively high STMP concentration (0.26 M) has promising structural and textural properties. This material exhibited excellent removal ability towards MB with a maximum adsorption capacity of about 992 mg/g for an initial pH of 10. The kinetic and isotherm modeling study revealed that the pseudo-second-order and Freundlich models fitted well the measured adsorption experimental data. The MB adsorption process onto the synthesized hydrogel is exothermic, feasible and spontaneous. It mainly includes electrostatic interaction and hydrogen bonds. These findings suggest that double-cross-linked alginate-based hydrogel can be considered as an attractive and potential adsorbent for an effective cationic dye removal from aqueous environments. The use of such a green adsorbent for the treatment of organic-pollutants-rich industrial wastewaters promotes sustainability and circular economy concepts.

Recent developments in metallic-nanoparticles-loaded biochars synthesis and use for phosphorus recovery from aqueous solutions. A critical review.

Phosphorus (P) represents a major pollutant of water resources and at the same time a vital element for human and plants. P recovery from wastewaters and its reuse is a necessity in order to compensate the current important depletion of P natural reserves. The use of biochars for P recovery from wastewaters and their subsequent valorization in agriculture, instead of synthetic industrial fertilizers, promotes circular economy and sustainability concepts. However, P retention by pristine biochars is usually low and a modification step is always required to improve their P recovery efficiency. The pre- or post-treatment of biochars with metal salts seems to be one of the most efficient approaches. This review aims to summarize and discuss the most recent developments (from 2020- up to now) in: i) the role of the feedstock nature, the metal salt type, the pyrolysis conditions, and the experimental adsorption parameters on metallic-nanoparticles-loaded biochars properties and effectiveness in recovering P from aqueous solutions, as well as the dominant involved mechanisms, ii) the effect of the eluent solutions nature on the regeneration ability of P-loaded biochars, and iii) the practical challenges facing the upscaling of P-loaded biochars production and valorization in agriculture. This review shows that the synthesized biochars through slow pyrolysis at relatively high temperatures (up to 700-800 °C) of mixed biomasses with Ca- Mg-rich materials or impregnated biomasses with specific metals in order to from layered double hydroxides (LDHs) biochars composites exhibit interesting structural, textural and surface chemistry properties allowing high P recovery efficiency. Depending on the pyrolysis's and adsorption's experimental conditions, these modified biochars may recover P through combined mechanisms including mainly electrostatic attraction, ligand exchange, surface complexation, hydrogen bonding, and precipitation. Moreover, the P-loaded biochars can be used directly in agriculture or efficiently regenerated with alkaline solutions. Finally, this review emphasizes the challenges concerning the production and use of P-loaded biochars in a context of circular economy. They concern the optimization of P recovery process from wastewater in real-time scenarios, the reduction of energy-related biochars production costs and the intensification of communication/dissemination campaigns to all the concerned actors (i.e., farmers, consumers, stakeholders, and policymakers) on the benefits of P-loaded biochars reuse. We believe that this review is beneficial for new breakthroughs on the synthesis and green application of metallic-nanoparticles-loaded biochars.

Lead removal from aqueous solutions by olive mill wastes derived biochar: Batch experiments and geochemical modelling.

In this study, lead removal from aqueous solutions using biochar derived from olive mill solid and liquid wastes has been investigated by applying batch experiments and geochemical modelling. The batch adsorption experiments included the assessment of several key parameters such as the contact time (kinetic), initial concentration (isotherm), pH, adsorbent dose, and the presence of competitive cations, whilst the geochemical modelling focused on the involved adsorption mechanisms using the PHREEQC code. The kinetic studies showed that lead adsorption is a relatively fast process, where intraparticle diffusion is the rate-limiting step. Biochar dose, solution pH and the presence of competitive ions significantly affected the Pb adsorption effectiveness by the biochar. Especially the higher Pb removal percentages were observed in mono-elemental solutions with high biochar dose at mildly acidic solution pH values. The maximum Pb adsorption capacity of biochar was estimated as 40.8 mg g-1 which is higher than various biochars derived from sludge, lignocellulosic and animal biomasses. On the other hand, the geochemical modelling employing the PHREEQC code showed that ion exchange and Pb precipitation are the main reactions controlling its removal from aqueous solutions, whilst surface complexation is insignificant, mainly due to the low surface functional groups on the used biochar.

The dairy biorefinery: Integrating treatment process for Tunisian cheese whey valorization.

In order to set up a cost-efficient biorefinery in a Tunisian dairy industry, the production unit effluents are recovered. The main objective is to develop an optimum method for the production of bioethanol from whey. An energy analysis as well as environmental and economic analyses are performed for a bioethanol production plant. Four production scenarios are examined in order to determine the most provident as well as the less polluting ones. The process and cost models were developed using SuperPro Designer software which a simulation program that is able to estimate both process and economic parameters. This software uses energy and mass balances. The model can be used to assess the efficiency, the resources consumption, the profitability and the environmental impact of each scenario. The results demonstrate that the third scenario, in which a reverse osmosis procedure is added to concentrate the whey, a continuous stoichiometric reaction procedure is integrated to model the biotransformation in the fermenter and where streams are added in order to recycle the biomass, produces the highest amount of bioethanol with 1.65 MT/year but the second one (where no streams were added) is the most profitable one with revenues as high as 570 000 $/year. The corresponding cost of ethanol production is 0.271 US $ ethanol per liter. The net present value (NPV) and the return on investment (ROI) of each scenario are positive. Such result indicates that all these investments could be undertaken in order to find an eco-friendly issue for the dairy industry effluents. Cheese whey could serve as an alternative raw material for producing ethanol.

Recent advancements on biochars enrichment with ammonium and nitrates from wastewaters: A critical review on benefits for environment and agriculture.

During the last decade, biochars have been considered as attractive and eco-friendly materials with various applications including wastewater treatment, energy production and soil amendments. However, the important nitrogen losses during biochars production using the pyrolysis process have limited their potential use in agriculture as biofertilizer. Therefore, it seems necessary to enrich these biochars with nitrogen sources before their use in agricultural soils. This paper is the first comprehensive review on the assessment of biomass type and the biochars' properties effects on N recovery efficiency from aqueous solutions as well as its release and availability for plants when applying the N-enriched chars in soils. In particular, the N recovery efficiency by raw biochars versus the type of the raw feedstock is summarized. Then, correlations between the adsorption performance and the main physico-chemical properties are established. The main mechanisms involved during ammonium (NH4-N) and nitrates (NO3-N) recovery process are thoroughly discussed. A special attention is given to the assessment of the biochars physico-chemical modification impact on their N recovery capacities improvement. After that, the application of these N-enriched biochars in agriculture and their impacts on plants growth as well as methane and nitrous oxide greenhouse gas emissions reduction are also discussed. Finally, the main future development and challenges of biochars enrichment with N from wastewaters and their valorization as biofertilizers for plants growth and greenhouse gas (GHG) emissions reduction are provided. This systematic review is intended to promote the real application of biochars for nutrients recovery from wastewaters and their reuse as eco-friendly fertilizers.

Fenton oxidation for soil remediation: A critical review of observations in historically contaminated soils.

Fenton-based treatments have received tremendous attention in recent decades as viable strategies for soil decontamination. Historically contaminated soils are characterized by particular contamination types, pollution composition patterns, soil constituents, and complex soil-pollutant interactions arising due to long-term pollutant aging. These major pitfalls dictate the remediation efficiency in a significantly different way in soils with a history of contamination than that in a spiked soil. It becomes, therefore, highly challenging to treat historically contaminated soils. Despite the immense amount of collected research data in these soils, to our knowledge, no comprehensive review of this topic has been published. This article is intended to provide a critical review of the applications, limitations, and implications of various Fenton-based processes exclusively in these soils. These processes are differentiated on the basis of experimental conditions, reaction chemistry, efficiency, and impacts on soil biota. These processes are critically evaluated to illustrate the promising techniques with a brief description of related challenges and their potential solutions. Moreover, coupling Fenton oxidation with other remediation techniques such as bioremediation, chemical reduction, and soil washing has also been discussed. The last part of this review describes the effects of these processes onto soil quality and native biota, and how they can be addressed. It is also highly demanding to identify the processes which are not likely to evolve in practice either due to their poor efficiency, treatment cost, or environmental impacts. Future critical research directions have been identified to promote research for the upscaling of this technique for real field application.

Variation of soil properties with sampling depth in two different light-textured soils after repeated applications of urban sewage sludge.

Semi-arid agricultural soils have increasingly been subjected to urban sewage sludge (USS) applications due to accelerated soil depletion and shortages in manure supply. Research studies addressing USS reuse have mostly been conducted in cropping systems and focused on changes in topsoil properties of a given texture. Therefore, sludge-soil interactions could be largely influenced by the presence of plants, soil particle composition and depth. In this field study, two agricultural soils (sandy, S and sandy loam, SL) received simultaneously four annual USS applications of 40, 80, and 120 t ha-1 year-1 in absence of vegetation. Outcomes showed the increase of carbon and macronutrients in both soils proportionally to USS dose especially in the topsoil profile (0-20 cm). Subsoil (20-40 cm) was similarly influenced by sludge rates, showing comparable variations of fertility parameters though at significant lower levels. The depth-dependent improvement of soil fertility in both layers enhanced the microbiological properties accordingly, with significant variations in soil SL characterized by a higher clay content than soil S. Besides, positive correlations between increases in sludge dose, salinity, trace metals, and enzyme activities in both soils indicate that excessive sludge doses did not cause soil degradation or biotoxic effects under the described experimental conditions. In particular and despite high geoaccumulation indices of Ni in both soils and profiles, the global concentrations of Cu, Ni, Pb, and Zn were still below threshold levels for contaminated soils. In addition, the maintenance of pH values within neutral range and the increase of organic matter content with respect to control would have further reduced metal availability in amended soils. Therefore, we could closely investigate the effects of texture and depth on the intrinsic resilience of each soil to cope with repetitive USS applications.

Optimization of hybrid treatment of olive mill wastewaters through impregnation onto raw cypress sawdust and electrocoagulation.

This research investigation proposes a new method for sustainable olive mill wastewater (OMW) treatment and handling. It is based on the combination of its impregnation onto raw cypress sawdust (RCS) followed by electrocoagulation. The retention of OMW compounds onto various RCS doses show an important decrease of its chemical oxygen demand (COD) and its main cation and anion content. The maximum retention efficiencies of COD, Na+, K+, Ca2+, Mg2+, Cl-, [Formula: see text], and [Formula: see text] were about 51.0%, 75.3%, 28.7%, 77.9%, 84.7%, 41.1%, 98.3%, and 90.9%, respectively, for the highest RCS dose (200 g L-1). This organic matter- and nutrient-loaded biomass could be thermochemically converted through pyrolysis into biofuel and biochar for energetic and agronomic purposes, respectively. The treatment by electrocoagulation of the pre-treated OMW using mild steel electrodes could be considered an attractive treatment method since 75.6% of COD removal efficiency was achieved. Besides, this approach permits a significant energy consumption reduction by 46% as compared with the electrocoagulation process alone. It allows also a significant improvement of the treated effluent quality in terms of both organic and mineral contents that could be reused for the irrigation of olive trees in the context of circular economy.

Biochar production from Cypress sawdust and olive mill wastewater: Agronomic approach.

Olive mill wastewater (OMW) is nowadays considered as a serious source pollution. At the same time, it contains high amounts of nutrients, especially potassium and phosphorus that could be recovered for agricultural purposes. The aim of the current experimental research work is to investigate the agronomic potential use of OMW based biochar produced from the slow pyrolysis at 500 °C of raw cypress sawdust (CS) impregnated with OMW (ICS-OMW-B). In order to understand the contribution of OMW, two additional biochars were produced from raw cypress sawdust (RCS-B) and cypress sawdust pretreated with potassium chloride (ICS-K-B). Results indicated that RCS impregnation by OMW significantly improved the produced biochar's chemical properties, especially its nutrients contents. Furthermore, in comparison with the other biochars, ICS-OMW-B application as an organic fertilizer showed promising results in terms of produced fresh and dry masses, as well as potassium bioavailability as assessed in test experiments with ryegrass. For instance, the dry matter masses of the rye-grass treated with ICS-OMW-B were about 23, 34 and 50 wt% higher than the ones measured for the tests using RCS-B, ICS-K-B and synthetic K-fertilizer as amendments, respectively. Besides, this biochar has a potential effect on the suppression of various pathogens existing in the tested agricultural soil. All these results demonstrated that the biochar generated from the slow pyrolysis of impregnated sawdust with OMW could be considered as attractive and promising organic fertilizer for acidic agricultural soils.

Application of olive mill waste-based biochars in agriculture: Impact on soil properties, enzymatic activities and tomato growth.

The olive oil industry is an important economic sector in Mediterranean countries. However, oil production is unfortunately accompanied by the generation of huge amounts of olive mill solid wastes (OMSW) and olive mill wastewater (OMWW). In the present study, a strategy is proposed for converting these olive mill wastes into biochar through pyrolysis, for their later use as an organic amendment in agriculture. Specifically, two biochars were prepared from the pyrolysis of OMSW at 500 °C, either alone or impregnated with OMWW (OMSW-B and I-OMSW-B). The characterization of the OMSW and I-OMSW samples and their derived biochars showed that the fixed carbon and ash contents in the feedstocks increased by 38% and 11% respectively for OMSW-B, and by 37% and 12% respectively for I-OMSW-B. Interestingly, the impregnation process significantly increased Na, P, K, Ca and Fe contents in the produced biochars. The effect of OMSW-B and I-OMSW-B amendments at different application dose (1%, 2.5% and 5% wt/wt) on the enzymatic activity of an agricultural soil was performed at laboratory scale with a pot test. The experimental results showed that phosphatase and urease activity increased with biochar application rate; amendment with I-OMSW-B at 1%, 2.5% and 5% enhanced the phosphatase activity by 63%, 142% and 285% and urease activity by 50%, 116% and 149%, respectively. On the other hand, dehydrogenase and protease activities were higher for the application rate of 2.5% biochar. Biochar amendment promoted tomatoes seedling growth after 10 weeks, which was highest in the application rates of 2.5% and 5% for both OMSW-B and I-OSMW-B. Thus, the produced biochars had great potential to be used as biofertilizers in agriculture.

Impact of urban sewage sludge on soil physico-chemical properties and phytotoxicity as influenced by soil texture and reuse conditions.

Urban sewage sludge (USS) is increasingly applied to agricultural soils, but mixed results have been reported because of variations in reuse conditions. Most field trials have been conducted in cropping systems, which conceal intrinsic soil responses to sludge amendments due to the rhizosphere effect and farming practices. Therefore, the current field study highlights long-term changes in bare soil properties in strict relationship with soil texture and USS dose. Two agricultural soils (loamy sand [LS] and sandy [S]) were amended annually with increasing sludge rates up to 120 t ha-1 yr-1 for 5 yr under unvegetated conditions. Outcomes showed a USS dose-dependent variation of all studied parameters in topsoil samples. Soil salinization was the most significant risk related to excessive USS doses. Total dissolved salts (TDS) in saturated paste extracts reached the highest concentrations of 37.2 and 43.1 g L-1 in S soil and LS soil, respectively, treated with 120 t USS ha-1 yr-1 . This was also reflected by electrical conductivity of the saturated paste extract (ECe ) exceeding 4,000 µS cm-1 in both treatments. As observed for TDS, fertility indicators and bioavailable metals varied with soil texture due to the greater retention capacity of LS soil owing to higher fine fraction content. Soil phytotoxicity was estimated by the seed germination index (GI) calculated for lettuce, alfalfa, oat, and durum wheat. The GI was species dependent, indicating different degrees of sensitivity or tolerance to increasing USS rates. Lettuce germination was significantly affected by changes in soil conditions showing negative correlations with ECe and soluble metals. In contrast, treatment with USS enhanced the GI of wheat, reflecting higher salinity tolerance and a positive effect of sludge on abiotic conditions that control germination in soil. Therefore, the choice of adapted plant species is the key factor for successful cropping trials in sludge-amended soils.

Olive mill wastewater: From a pollutant to green fuels, agricultural and water source and bio-fertilizer - Hydrothermal carbonization.

Hydrothermal carbonization (HTC) is considered as a promising technique for wastes conversion into carbon rich materials for various energetic, environmental and agricultural applications. In this work, the HTC of olive mill wastewater (OMWW) was investigated at different temperatures (180-220 °C) and both, the solid (i.e., hydrochars) and the final process liquid derived from the thermal conversion process were deeply analyzed. Results showed that the solid yield was affected by the temperature, i.e., decrease from 57% to 25% for temperatures of 180 °C and 220 °C, respectively. Furthermore, the hydrochars presented an increasing fixed carbon percentage with the increase of the carbonization temperature, suggesting that decarboxylation is the main reaction driving the HTC process. The decrease in the O/C ratio promoted an increase of the high heating value (HHV) by 32% for hydrochar prepared at 220 °C. The process liquids were sampled and their organic contents were analyzed using GC-MS technique. Acids, alcohols, phenols and sugar derivatives were detected and their concentrations varied with carbonization temperatures. The assessment of the physico-chemical properties of the generated HTC by-products suggested the possible application of the hydrochars for energetic insights while the liquid fraction could be practical for in agricultural field.

Phosphorus and ammonium removal characteristics from aqueous solutions by a newly isolated plant growth-promoting bacterium.

An indigenous plant growth-promoting bacterium isolated from Peganum Harmala rhizosphere in the arid ecosystem was found to solubilize and accumulate phosphates. This isolate was identified as Pseudomonas sp. (PHR6) by partial 16S rRNA gene sequence analysis. Controlled batch experiments on nutrients removal by this isolate in mineral medium showed relatively high efficiencies after 24 h of aerobic incubation with average values of 117.59 and 335.38 mg gVSS-1 for phosphorus (P-PO4) and nitrogen (N-NH4), respectively. Furthermore, the strain performed heterotrophic nitrification ranging from 48.81% to 84.24% of the total removed nitrogen. On the other hand, the experimental results showed that a short idle period (24 h) significantly enhanced P accumulation (up to 95%) and N assimilation (up to 50%) of the total removed amounts. However, long idle period (20 days) revealed firstly aerobic phosphorous release phase succeeded by another removal one within 24 h of incubation. Overall, the idle treatment enhances P removal efficiency from the mineral liquid medium without significant effects on N-NH4 removal performance. The isolated strain showed also significant nutrient removal ability from synthetic wastewater providing an accumulated fraction of 98% from the total removed phosphorus amount. This study highlights the potential contribution of the selected rhizobacterium PHR6 to both environmental nutrient recycling and pollution control especially regarding phosphorus.

Comparative study of electrochemical hybrid systems for the treatment of real wastewaters from agri-food activities.

Agri-food wastewaters are characterized by high contents of hardly biodegradable organics and large amounts of inorganics especially nitrogen and phosphorus. The present work investigates the efficiency of two electrochemical treatment processes, namely electrochemical oxidation/reduction (EOR), electrocoagulation (EC) and their combination for the treatment of two types of effluents collected from poultry slaughterhouse (SHWW) and dairy (DWW) industries. The optimization of these treatment systems in terms of pollutant performance removal and energy cost were carried out. The EOR treatment was assessed on a bipolar cell with Boron-Doped Diamond (BDD) supported on silicon electrodes. While, the EC treatment was performed on a reactor containing mild steel electrodes with parallel configuration. The simultaneous removal efficiencies of the organic matter in term of the chemical oxygen demand (COD), nitrates, ammonium/ammonia and phosphates, as well as the electric energy consumption (EEC), were evaluated for the different electrochemical scenarios. Results indicated that the EOR treatment shows the highest removal efficiencies of COD, nitrates and ammonia from the two studied wastewaters. While, the phosphates were removed only by the EC process. On the other hand, the EC process shows a relatively low cost in term of EEC (0.01 kWh/g COD-1), which is about 13 times lower than the one consumed during the EOR process. The combination of the two processes leads to the improvement of the removal rate of all coexistent pollutants when the EC technology was used as a pre-treatment step. While, this coupling mode has the highest EEC. However, when the EOR process was used before the EC one, the removal rates of COD and nitrates were globally similar to the EOR process alone with a relatively low EEC.

Investigations on phosphorus recovery from aqueous solutions by biochars derived from magnesium-pretreated cypress sawdust.

The ability of biochars, derived from the pyrolysis at 400 °C; 500 °C and 600 °C of pretreated cypress sawdust with 20 wt% magnesium chloride (MgCl2) solutions, in recovering phosphorus from aqueous solutions was investigated under various experimental conditions in batch mode. The experimental results indicated that cypress sawdust pretreatment with MgCl2 induced important modifications of the physical and chemical biochars' properties favoring phosphorus recovery from the used synthetic solutions. Moreover, phosphorus recovery efficiency increased with the increase of the used pyrolysis temperature. Indeed, for an aqueous pH of 5.2 and a phosphorus concentration of 75 mg L-1, the recovered amounts increased from 19.2 mg g-1 to 33.8 mg g-1 when the used pyrolysis temperature was raised from 400 °C to 600 °C. For all the tested biochars, the phosphorus recovery kinetics data were well fitted by the pseudo-second-order model, and the equilibrium state was obtained after 180 min of contact time. Furthermore, the phosphorus recovery data at equilibrium were well described by the Langmuir model with a maximal recovery capacity of 66.7 mg g-1 for the magnesium pretreated biochar at 600 °C. Phosphorus recovery by the used biochars occurred probably through adsorption onto biochars' active sites as well as precipitation with magnesium ions as magnesium phosphates components. All these results suggested that biochars derived from MgCl2 pretreated cypress sawdust could be considered as promising materials for phosphorus recovery from wastewaters for a possible further subsequent use in agriculture as amendments.

Alkaline-treated sawdust as an effective material for cationic dye removal from textile effluents under dynamic conditions: breakthrough curve prediction and mechanism exploration.

This paper deals with the methylene blue molecule (MB) removal from synthetic and real textile wastewaters by alkali-treated orange tree sawdust (ATOS) under different dynamic conditions. Experimental results showed that MB removal efficiencies by ATOS increased when increasing initial dye concentrations and bed depths but decreased with the increase of the applied flow rates with a maximum adsorption capacity of about 110 mg g-1. Moreover, various empirical models were applied to predict the experimental breakthrough curves (BTCs) and to determine the characteristic adsorption parameters. The applied models successfully fitted data in the following order: Thomas ([Formula: see text] = 0.969), dose response ([Formula: see text] = 0.949), and Clark ([Formula: see text] = 0.874). ATOS was also found to efficiently remove dyes and other mineral pollutants such as chlorides, nitrates, and phosphates from real wastewaters. MB removal by ATOS involved not only cationic exchange but also complexation with acidic and basic functional groups. Moreover, important MB desorption yields from ATOS (more than 93%) were obtained when using saline solutions. All these results confirmed that NaOH-treated orange tree sawdust can be considered as a promising material for the removal of cationic dyes from industrial wastewaters.

Optimization of a cationic dye removal by a chemically modified agriculture by-product using response surface methodology: biomasses characterization and adsorption properties.

The present study investigates the alkaline modification of raw orange tree sawdust (ROS) for an optimal removal of methylene blue (MB), as a cationic dye model, from synthetic solutions. The effects of operating parameters, namely, sodium hydroxide (NaOH) concentrations, ROS doses in NaOH solutions, stirring times, and initial MB concentrations on dye removal efficiency, were followed in batch mode. The process optimization was performed through the response surface methodology approach (RSM) by using Minitab17 software. The results showed that the order of importance of the followed parameters was NaOH treatment concentrations > stirring times > initial MB concentrations > ROS doses in NaOH solutions. The optimal experimental conditions ensuring the maximal MB removal efficiency was found for a NaOH treatment concentration of 0.14 M, a stirring time of 1 h, a ROS dose in NaOH solutions of 50 g L-1, and an initial MB concentration of 69.5 mg L-1. Specific analyses of the raw and alkali-treated biomasses, e.g., SEM/EDS and XRD analyses, demonstrated an important modification of the crystalline structure of the wooden material and a significant increase in its surface basic functional groups. Kinetic and isotherm studies of MB removal from synthetic solutions by ROS and the alkali-treated material (ATOS) showed that for both adsorbents, the pseudo-second-order and Langmuir model fitted the best the experimental data, respectively, which indicates that MB removal might be mainly a chemical and a monolayer process. Furthermore, thanks to the chemical modification of the ROS, the MB maximal uptake capacity has increased from about 39.7 to 78.7 mg g-1. On the other hand, due to the competition phenomenon, the coexistence of MB and Zn(II) ions could significantly decrease the MB removal efficiency. A maximal decrease of about 32 % was registered for an initial Zn(II) concentration of 140 mg L-1. Desorption experiments undertaken at natural pH (without adjustment: pH = 6) and with different NaCl concentrations emphasized that the adsorbed MB could be significantly desorbed from both the tested materials, offering their possible reuse as efficient adsorbents. All these results confirmed that NaOH-treated orange tree sawdust could be considered as an efficient, economic, and ecological alternative for the removal of cationic dyes from industrial wastewaters.

Lead removal from aqueous solutions by raw sawdust and magnesium pretreated biochar: Experimental investigations and numerical modelling.

Lead removal from aqueous solutions by raw cypress (Cupressus sempervirens L.) sawdust (RCS) and its derivative magnesium pretreated biochar (Mg-B) was investigated under static and dynamic conditions through batch and column assays. The Hydrus-1D model was used to estimate the transport parameters of the lead measured breakthrough curves. The batch experiments results showed that Mg-B was very efficient in removing lead compared to RCS and several other previously tested natural and modified materials. The column experiments results indicated that for both RCS and Mg-B, lead breakthrough curves and the related removal efficiencies were mainly dependent on the used initial concentration and the adsorbents bed height. The use of Hydrus-1D showed that the two-site chemical non-equilibrium model describes better the experimental lead breakthrough curves for both RCS and Mg-B as the equilibrium model.