Dye Sorption from Mixtures on Chitosan Sorbents.

This article presents studies on the sorption of the anionic dyes Reactive Black 5 (RB5) and Reactive Yellow 84 (RY84) from solutions of single dyes and from dye mixtures onto three chitosan sorbents-chitin, chitosan DD75% and chitosan DD95%. In this work, the influence of pH on sorption efficiency, the sorption equilibrium time for the tested anionic dyes and the sorption capacity in relation to the individual dyes and their mixtures were determined. It has been found that the sorption process for both dyes was most effective at pH 3 for chitin and chitosan DD75 and at pH 4 for chitosan DD95%. The obtained results were described by the double Langmuir equation (Langmuir 2). The obtained constants made it possible to determine the affinity of the tested dyes for the three sorbents and the sorption capacity of the sorbents. For RB5, the highest sorption capacity for chitosan DD95% was achieved with sorption from a single solution-of 742 mg/g DM and with sorption from mixed dyes-of 528 mg/g DM. For RY84, the highest efficiency was also achieved for chitosan DD95% and was 760 mg/g DM for a single dye solution and 437 mg/g DM for a mixture of dyes.

Aminated Rapeseed Husks (Brassica napus) as an Effective Sorbent for Removing Anionic Dyes from Aqueous Solutions.

The study investigated the effect of modifying rapeseed husks with ammonia and epichlorohydrin on their sorption capacity against anionic reactive dyes: Reactive Black 5 (RB5) and Reactive Yellow 84 (RY84). Its scope included sorbents characterization (FTIR, pHPZC), determination of pH influence on the sorption effectiveness of dyes, the adsorption kinetics of dyes, as well as the maximum sorption capacity. The study proved that the reaction of rapeseed husk biomass with ammonia can lead to its amination, namely to the introduction of amine functional groups into the material's structure. The sorption effectiveness of RB5 and RY84 on the tested sorbents was the highest in the pH range of 2-3. The dye sorption kinetics was well described by the pseudo-second-order model. The sorption equilibrium time ranged from 90 to 180 min, and depended on the initial concentration of dyes and the number of amino groups on the sorbent's surface. The most efficient of the sorbents tested were rapeseed husks pre-activated with epichlorohydrin and then aminated with ammonia. Their sorption capacity determined for RB5 and RY84 was 135.83 mg/g and 114.23 mg/g, respectively, which was 794% and 737% higher than that of the non-modified husks.

The Use of Chitin for the Removal of Nitrates and Orthophosphates from Greenhouse Wastewater.

The study investigated the possibility of using chitin flakes as an unconventional sorbent for the removal of orthophosphates and nitrates from greenhouse wastewater (GW). The effluent parameters were as follows: 66.2 mg P-PO4/L, 566.0 mg N-NO3/L, 456.0 mg S-SO4/L, 13.7 mg Cl-/L, 721 mg Ca2+/L, 230 mg Mg2+/L, hardness 11.3 °dH, and pH 5.4. The scope of the research included determinations of the influence of pH on GW composition and the efficiency of nutrient sorption, the kinetics of nutrient sorption, the influence of the dose of chitin flakes on the effectiveness of nutrient binding and the maximum sorption capacity of the sorbent. The sorption of P-PO4 on the tested sorbent was most effective at pH 4, and the sorption of N-NO3 at pH 2. The equilibrium time of sorption of both nutrients from GW to chitin depended on the sorbent dose and ranged from 150 to 180 min. The sorbent dose of 40 g/L enabled removing 90% of orthophosphates and 5.7% of nitrates from the wastewater. The maximum sorption capacity of CH towards P-PO4 and N-NO3 contained in the GW was 3.20 mg/g and 3.04 mg/g, respectively. In turn, the sorption of calcium and magnesium ions on chitin flakes was completely ineffective.

The Use of Various Types of Waste Paper for the Removal of Anionic and Cationic Dyes from Aqueous Solutions.

This study examined the possibility of using various types of waste paper-used newsprint (NP), used lightweight coated paper (LWC), used office paper (OP), and used corrugated cardboard (CC)-for the removal of anionic dyes, Acid Red 18 (AR18) and Acid Yellow 23 (AY23), and cationic dyes, Basic Violet 10 (BV10) and Basic Red 46 (BR46), from aqueous solutions. The scope of this research included the characterization of sorbents (FTIR, SEM, BET surface area, porosity, pHPZC, effectiveness of water coloration), determination of pH effect on the effectiveness of dye sorption, sorption kinetics (pseudo-first-order model, second-order model, intraparticular diffusion model), and the maximum sorption capacity (Langmuir models and Freundlich model) of the tested sorbents. The use of waste paper materials as sorbents was found to not pose any severe risk of aquatic environment contamination. AR18, AY23, and BV10 sorption intensities were the highest at pH 2, and that of RB46 at pH 6. The waste paper sorbents proved particularly effective in removing cationic dyes, like in the case of, e.g., NP, which had a sorption capacity that reached 38.87 mg/g and 90.82 mg/g towards BV10 and BR46, respectively, and were comparable with that of selected activated carbons (literature data).

Effect of the C:N:P ratio on the denitrifying dephosphatation in a sequencing batch biofilm reactor (SBBR).

A series of investigations were conducted using sequencing batch biofilm reactor (SBBR) to explore the influence of C:N:P ratio on biological dephosphatation including the denitrifying dephosphatation and the denitrification process. Biomass in the reactor occurred mainly in the form of a biofilm attached to completely submerged disks. Acetic acid was used as the source of organic carbon. C:N:P ratios have had a significant effect on the profiles of phosphate release and phosphate uptake and nitrogen removal. The highest rates of phosphate release and phosphate uptake were recorded at the C:N:P ratio of 140:70:7. The C:N ratio of 2.5:1 ensured complete denitrification. The highest rate of denitrification was achieved at the C:N:P ratio of 140:35:7. The increase of nitrogen load caused an increase in phosphates removal until a ratio C:N:P of 140:140:7. Bacteria of the biofilm exposed to alternate conditions of mixing and aeration exhibited enhanced intracellular accumulation of polyphosphates. Also, the structure of the biofilm encouraged anaerobic-aerobic as well as anoxic-anaerobic and absolutely anaerobic conditions in a SBBR. These heterogeneous conditions in the presence of nitrates may be a significant factor determining the promotion of denitrifying polyphosphate accumulating organism (DNPAO) development.

The Effect of Modifying Canadian Goldenrod (Solidago canadensis) Biomass with Ammonia and Epichlorohydrin on the Sorption Efficiency of Anionic Dyes from Water Solutions.

This study examined the effect of modifying Canadian goldenrod (Solidago canadensis) biomass on its sorption capacity of Reactive Black 5 (RB5) and Reactive Yellow 84 anionic dyes. The scope of the research included the characteristics of sorbents (FTIR, elementary analysis, pHPZC), the effect of pH on dye sorption efficiency, sorption kinetics, and the maximum sorption capacity (describing the data with Langmuir 1 and 2 and Freundlich models). FTIR analyses showed the appearance of amine functional groups in the materials modified with ammonia water, which is indicative of the sorbent amination process. The amination efficiency was higher in the case of materials pre-activated with epichlorohydrin, which was confirmed by elemental analysis and pHPZC values. The sorption efficiency of RB5 and RY84 on the tested sorbents was the highest in the pH range of 2-3. The sorption capacity of the goldenrod biomass pre-activated with epichlorohydrin and then aminated with ammonia water was 71.30 mg/g and 59.29 mg/g in the case of RB5 and RY84, respectively, and was higher by 2970% and 2510%, respectively, compared to the unmodified biomass. Amination of biomass pre-activated with epichlorohydrin can increase its sorption capacity, even by several dozen times.

Recovery of phosphorus and other minerals from greenhouse wastewater generated during soilless tomato cultivation by means of alkalizing agents.

The research was aimed at determining the possibility of recovering part of nutrients by precipitation from greenhouse wastewater (GW) from soilless tomato cultivation. Analyses included such elements as: P, S, N, Cl, Ca, Mg, K, Mo, Mn, Fe, Zn, Cu, and B. Three alkalizing agents were tested in a pH range of 6.5-12.0: Ca(OH)2, KOH, and NH4OH, which simultaneously enrich greenhouse wastewater in calcium, potassium, and nitrogen. It was determined what dose of the alkalizing agent should be used, how the composition of the treated GW will change, how much and what kind of sludge will be formed, what will be the stability and technical possibility of sediment separation, and whether the type of alkalizing agent affects the course of the process. Precipitation triggered by the alkalizing agents proved to be an effective method for the recovery of phosphorus, calcium, magnesium, manganese, and boron, while it turned out ineffective in the case of the other elements tested, including nitrogen and potassium. Phosphorus recovery depended mainly on GW pH and forms of phosphate ions corresponding to this pH, and not on the alkalizing agent type. The pH value adjustment to pH = 9 for KOH and NH4OH and to pH = 9.5 for Ca(OH)2 ensured <99 % phosphorus recovery, which corresponded to P concentration in GW below 1 mgP/L and to the applied Ca(OH)2, KOH, and NH4OH doses of 0.20 g/L, 0.28 g/L, and 0.08 g/L, respectively. The highest P contents in the sludge were determined at pH = 7 and reached 18.0 %, 16.8 %, and 16.3 % in the experimental series with Ca(OH)2, KOH, and NH4OH, respectively. The sludge volume index increase along with pH increase up to pH = 10.5 for KOH and to pH = 11 for Ca(OH)2 and NH4OH.

The Use of Chitin from the Molts of Mealworm (Tenebrio molitor) for the Removal of Anionic and Cationic Dyes from Aqueous Solutions.

The possibility of using chitin from the molts of an insect-ealworm (Tenebrio molitor) to remove anionic (RB5, RY84) and cationic dyes (BV10, BR46) from aqueous solutions was investigated. The scope of the research included, among others: Characteristics of chitin from mealworms (FTIR, SEM, pHPZC), the effect of pH on sorption efficiency, sorption kinetics (pseudo-first, pseudo-second order, intramolecular diffusion models) and the determination of the maximum sorption capacity (Langmuir and Freundlich models). The sorption efficiency of anionic dyes on chitin from mealworm was the highest at pH 2-3, and for cationic dyes at pH 6. The equilibrium time of sorption of anionic dyes was 240-300 min and for cationic dyes it was 180-240 min. The experimental data on dye sorption kinetics was best described by the pseudo-second order model. The maximum sorption capacity of chitin from the mealworm for the anionic dyes RB5 and RY84 was 121.15 mg/g and 138.55 mg/g, respectively, and was higher than with some carbon-based materials (literature data). In the case of cationic dyes, the sorption capacity of the tested chitin was lower and reached 3.22 mg/g and 59.56 mg/g for BV10 and BR46, respectively.

The use of air-lift adsorber with a floating filling from a cross-linked chitosan hydrogels for Reactive Black 5 removal.

This work substantially extends knowledge on the possibilities of treating colored industrial wastewater via sorption under flow conditions. The presented study aimed to determine the effectiveness of Reactive Black 5 (RB5) dye sorption from aqueous solutions under dynamic (flow) conditions in an unconventional air-lift type loop reactor with a filling made of hydrogel chitosan sorbents. The dye was removed from mono-component solutions (deionized water + RB5) and synthetic dyeing wastewater containing RB5 dye, NaCl (3 g/L), and an anti-creasing agent-UNICREASE JET (2 g/L). The sorbents tested in the study included: unmodified chitosan (CHs), chitosan ionically cross-linked with sodium citrate (CHs-CIT), and chitosan covalently cross-linked with epichlorohydrin (CHs-ECH). Each experimental series aimed to determine: the bed break-through time (CE = 0.1 C0), time of depletion of the sorbent's sorption properties (CE = C0), and maximal sorption capacity of the sorbents (Qmax). The data obtained under dynamic conditions were described using Thomas, Yoon-Nelson, and Bohart-Adams models. The volume of the solution effectively treated in the air-lift reactor was significantly affected by chitosan sorbent type. At C0 = 50 mg RB5/L, the adsorber with the filling made of 1 g d.m. CHs allowed for the effective treatment of 4.6 L of synthetic wastewater (Qmax = 1504.7 mg/g), whereas CHs-ECH ensured 34.6 L of the treated solution (Qmax = 3212.9 mg/g).

The use of spent coffee grounds and spent green tea leaves for the removal of cationic dyes from aqueous solutions.

This study aimed to examine sorption effectiveness of cationic dyes: Basic Red 46 (BR46) and Basic Violet 10 (BV10) onto spent coffee ground (CG) and spent green tea leaves (GTL). The scope of the study included, i.a.: sorbent FTIR spectra analysis, determination of pH effect on dye sorption effectiveness, analysis of dye sorption kinetics, and determination of maximal sorption capacity of the sorbents. The effectiveness of BR46 sorption on the sorbents tested was the highest at pH 6 and that of BV10 at pH 3. Both sorbents caused changes in solution pH during the sorption process, due to the system tending to reach the pH value approximating the pHZPC (pHPZC = 7.55 for CG and pHPZC = 7.05 for GTL). The time needed to reach BR46 and BV10 sorption equilibrium onto CG and GTL ranged from 180 to 240 min. The intramolecular diffusion model demonstrated that the sorption of cationic dyes onto CG and GTL proceeded in three phases differing in the intensity and duration. The maximal sorption capacity of CG reached 179.4 mg/g for BR46 and 59.3 mg/g for BV10. The sorption capacity of GTL was lower and reached 58.0 mg/g for BR46 and 26.7 mg/g for BV10.

Recovery of phosphorus as soluble phosphates from aqueous solutions using chitosan hydrogel sorbents.

This manuscript presents new method of phosphorus recovery from aqueous solutions in a convenient form of readily-soluble phosphates using chitosan hydrogels. Non-modified chitosan hydrogel granules (CHs) and chitosan hydrogel granules crosslinked with epichlorohydrin (CHs-ECH) served as orthophosphate ion carriers. The developed method was based on cyclic sorption/desorption of orthophosphates, with desorption performed in each cycle to the same solution (the concentrate). The concentrations of orthophosphates obtained in the concentrates depended on, i.a., sorbent type, sorption pH, source solution concentration, and desorption pH. Phosphorus concentrations in the concentrates were even 30 times higher than these in the source solutions. The maximum concentrate concentrations reached 332.0 mg P-PO4/L for CHs and 971.6 mg P-PO4/L for CHs-ECH. The experimental series with CHs-ECH were characterized by higher concentrations of the obtained concentrate, however the concentrates were also more contaminated with Cl- and Na+ ions compared to series with CHs. The high content of chlorine and sodium ions in the concentrates was also favored by the low pH of sorption (pH < 4) and very high pH of desorption (pH > 12) in the cycles. After concentrate evaporation, phosphorus content in the sediment ranged from 17.81 to 19.83% for CHs and from 16.04 to 17.74% for CHs-ECH.

The share of electrochemical reduction, hydrogenotrophic and heterotrophic denitrification in nitrogen removal in rotating electrobiological contactor (REBC) treating wastewater from soilless cultivation systems.

There is a growing global environmental problem of agricultural wastewater from soilless plant cultivation systems. In most countries dominate open fertilization systems, in which excess of nutrient solution is discharged in an uncontrolled way into the ground inside greenhouses or adjacent areas. Wastewater from such systems is characterized by a very high concentration of nitrogen and phosphorus compounds and their discharge into the environment causes significant pollution of the water and soil environment. The goal of the research was to determine the contribution of electrochemical reduction of nitrogen, hydrogenotrophic and heterotrophic denitrification in the process of nitrogen removal in a rotating electrobiological contactor (REBC) depending on hydraulic retention time (HRT) and electric current density (J). Synthetic sewage with characteristics corresponding to wastewater from soilless cultivation of tomatoes was the subject of the research. The first part of the experiment included determination of the effect of HRT on the effectiveness of bio-processes of nutrients removal in a rotating biological contactor (RBC). The second concerned the effect of HRT and J on the effectiveness of nutrients removal in a rotating electrochemical contactor (RECC), while the third part - the effect of HRT and J on the effectiveness of nutrients removal in REBC. RBC was characterized by low efficiency of denitrification (6.2 to 9.2%). The effectiveness of nitrogen removal in RECC was determined by both electric current density and hydraulic retention time. The highest efficiency was 53.4%. REBC nitrogen removal effectiveness was higher than in RBC and in RECC. The nitrogen removal efficiency increased along with increasing values of HRT, reaching the maximum value of 68.6% for J=10.0A/m2 and HRT=24h. The contribution of hydrogenotrophic denitrification in total nitrogen removal increased with the increase of electric current density.

Hydrogel chitosan sorbent application for nutrient removal from soilless plant cultivation wastewater.

In this study, we determined the effectiveness of removal of nutrients (nitrates and orthophosphates) from greenhouse wastewaters (GW) using non-cross-linked chitosan (CHs) and chitosan cross-linked with epichlorohydrin (CHs-ECH) in the form of hydrogel beads. GW used in the study had the following parameters: N-NO3 621.1 mg/L, P-PO4 60.8 mg/L, SO42- 605.0 mg/L, Cl- 0.9 mg/L, Ca2+ 545.0 mg/L, Mg2+ 178.0 mg/L, K+ 482.0 mg/L, hardness 113° dH, and pH 6.2. The scope of the study included determination of the effect of pH on wastewater composition and effectiveness of nutrient sorption, analyses of nutrient sorption kinetics, and analyses of the effect of sorbent dose on percentage removal of nutrients from GW. CHs-ECH was able to sorb 79.4% of P-PO4 and 76.7% of N-NO3 from GW, whereas CHs to remove 92.8% of P-PO4 and 53.2% of N-NO3.

Effect of the form and deacetylation degree of chitosan sorbents on sorption effectiveness of Reactive Black 5 from aqueous solutions.

The article presents the impact of a chitosan sorbent form (flakes/hydrogel granules) and the degree of its deacetylation (DD=75%/DD=85%/DD=90%) on the effectiveness of sorption of a popular textile dye Reactive Black 5 (RB5). The effect of pH on dye sorption effectiveness was examined as well as RB5 sorption kinetics and RB5 sorption capacity of the chitosan sorbent were tested. The highest sorption capacity (1559.7mg/g) was obtained for the chitosan hydrogel in the form of granules (DD=90%). Due to a loose structure and an easy access to sorption centers, chitosan hydrogel granules may ensure up to 224% higher sorption capacity (QDD75%=1307.5mg/g) than chitosan in the form of flakes (QDD75%=403.4mg/g). The sorption effectiveness of the tested dye was observed to increase in the range of DD=75%

The use of cross-linked chitosan beads for nutrients (nitrate and orthophosphate) removal from a mixture of P-PO4, N-NO2 and N-NO3.

A hydrogel chitosan sorbent ionically cross-linked with sodium citrate and covalently cross-linked with epichlorohydrin was used to remove nutrients from an equimolar mixture of P-PO4, N-NO2 and N-NO3. The scope of the study included, among other things, determination of the influence of pH on nutrient sorption effectiveness, nutrient sorption kinetics as well as determination of the maximum sorption capacity of cross-linked chitosan sorbents regarding P-PO4 (H2PO4-, HPO42-), N-NO2 (HNO2, NO2-), and N-NO3 (NO3-). The effect of the type of the cross-linking agent on the affinity of the modified chitosan to each nutrient was studied as well. The kinetics of nutrient sorption on the tested chitosan sorbents was best described with the pseudo-second order model. The model of intramolecular diffusion showed that P-PO4, N-NO2 and N-NO3 sorption on cross-linked hydrogel chitosan beads proceeded in two phases. The best sorbent of nutrients turned out to be chitosan cross-linked covalently with epichlorohydrin; with P-PO4, N-NO2 and N-NO3 sorption capacity reaching: 1.23, 0.94 and 0.76mmol/g, respectively (total of 2.92mmol/g). For comparison, the sorption capacity of chitosan cross-linked ionically with sodium citrate was: 0.43, 0.39 and 0.39mmol/g for P-PO4, N-NO2 and N-NO3, respectively (total of 1.21mmol/g).

Municipal landfill leachate nitrification in RBC biofilm - process efficiency and molecular analysis of microbial structure.

Landfill leachates were treated using a two-stage rotating biological contactor (RBC). At an ammonium load of 1.92gN-NH(4)/m(2)d, complete nitrification was obtained at the first stage; however, at a higher load (3.6gN-NH(4)/m(2)d) a two-stage system was needed to obtain complete nitrification. A further increase in the ammonium load to 4.79gN-NH(4)/m(2)d and 6.63gN-NH(4)/m(2)d caused a decrease of overall nitrification efficiency to 74.4% and 71.6%, respectively. Randomly amplified DNA analysis of bacteria present in the RBC revealed that the bacterial community differed over time. Regardless of the ammonium load, Nitrosomonas europaea and Nitrosomonas eutropha were the dominating species. The performed analyses provide a clear picture of bacterial population changes in response to changes of ammonium load during landfill leachate treatment.