This study investigated chlorinated transformation products (TPs) and their parent micropollutants, aromatic pharmaceuticals and personal care products (PPCPs) in the urban water bodies of two metropolitan cities. Nine PPCPs and 16 TPs were quantitatively or semi-quantitatively determined using isotope dilution techniques and liquid chromatography-tandem mass spectrometry. TPs and most PPCPs were effectively removed by conventional wastewater treatments in a wastewater treatment plant (WWTP). Chlorinated parabens and all PPCPs (at concentrations below 1000 ng/L) were present in the waters receiving treated wastewater. By contrast, the waters receiving untreated wastewater contained higher levels of PPCPs (up to 9400 ng/L) and more species of chlorinated TPs including chlorinated parabens, triclosan, diclofenac, and bisphenol A. The very different chemical profiles between the water bodies of the two cities of similar geographical and climatic properties may be attributed to their respective uses of chemicals and policies of wastewater management. No apparent increase in the number of species or abundances of TPs was observed in either the chlorinated wastewater or the seawater rich in halogens. This is the first study to elucidate and compare the profiles of multiple TPs and their parent PPCPs in the water bodies of coastal cities from tropical islands. Our findings suggest that chlorinated derivatives of bisphenol A, diclofenac, triclosan, and parabens in the surface water originate from sources other than wastewater disinfection or marine chlorination. Although further studies are needed to identify the origins, conventional wastewater treatments may protect natural water bodies against contamination by those chlorinated substances.
Heavy metal contamination in aqueous system has attracted global attention due to the toxicity and carcinogenicity effects towards living bodies. Among available removal techniques, adsorptive removal by nanosized materials such as metal oxide, metal organic frameworks, zeolite and carbon-based materials has attracted much attention due to the large active surface area, large number of functional groups, high chemical and thermal stability which led to outstanding adsorption performance. However, the usage of nanosized materials is restricted by the difficulty in separating the spent adsorbent from aqueous solution. The shift towards the use of adsorptive composite membrane for heavy metal ions removal has attracted much attention due to the synergistic properties of adsorption and filtration approaches in a same chamber. Thus, this review critically discusses the development of nanoadsorbents and adsorptive nanocomposite membranes for heavy metal removal over the last decade. The adsorption mechanism of heavy metal ions by the advanced nanoadsorbents is also discussed using kinetic and isotherm models. The challenges and future prospect of adsorptive membrane technology for heavy metal removal is presented at the end of this review.
Oily wastewater, especially water-oil emulsion has become serious environmental issue and received global attention. Chemical demulsifiers are widely used to treat oil-water emulsion, but the toxicity, non-recyclable and non-environmental friendly characteristic of chemical demulsifiers had limited their practical application in oil-water separation. Therefore, it is imperative to develop an efficient, simple, eco-friendly and recyclable demulsifiers for breaking up the emulsions from the oily wastewater. In this study, a magnetic demulsifier, magnetite-reduced graphene oxide (M-rGO) nanocomposites were proposed as a recyclable demulsifier to break up the surfactant stabilized crude oil-in-water (O/W) emulsion. M-rGO nanocomposites were prepared via in situ chemical synthesis by using only one type Fe salt and GO solid as precursor at room temperature. The prepared composites were fully characterized by various techniques. The effect of demulsifier dosage and pH of emulsion on demulsification efficiency (ED) has been studied in detailed. The demulsification mechanism was also proposed in this study. Results showed that M-rGO nanocomposites were able to demulsify crude O/W emulsion. The ED reaches 99.48% when 0.050 wt.% of M-rGO nanocomposites were added to crude O/W emulsion (pH = 4). Besides, M-rGO nanocomposites can be recycled up to 7 cycles without showing a significant change in terms of ED. Thus, M-rGO nanocomposite is a promising demulsifier for surfactant stabilized crude O/W emulsion.
Microalgal-bacterial granular sludge (MBGS) process has become a focal point in treating municipal wastewater. However, it remains elusive whether the emerging process can be applied for the treatment of aquaculture wastewater, which contains considerable concentrations of nitrate and nitrite. This study evaluated the feasibility of MBGS process for aquaculture wastewater treatment. Result showed that the MBGS process was competent to remove respective 64.8%, 84.9%, 70.8%, 50.0% and 84.2% of chemical oxygen demand, ammonia-nitrogen, nitrate-nitrogen, nitrite-nitrogen and phosphate-phosphorus under non-aerated conditions within 8 h. The dominant microalgae and bacteria were identified to be Coelastrella and Rhodobacteraceae, respectively. Further metagenomics analysis implied that microbial assimilation was the main contributor in organics, nitrogen and phosphorus removal. Specifically, considerable nitrate and nitrite removals were also obtained with the synergy between microalgae and bacteria. Consequently, this work demonstrated that the MBGS process showed a prospect of becoming an environmentally friendly and efficient alternative in aquaculture wastewater treatment.
The presence of dyes in the aquatic environment as a result of anthropogenic activities, especially textile industries, is a critical environmental challenge that hinders the availability of potable water. Different wastewater treatment approaches have been used to remediate dyes in aquatic environments; however, most of these approaches are limited by factors ranging from high cost to the incomplete removal of the dyes and contaminants. Thus, the use of adsorption as a water treatment technology to remove dyes and other contaminants has been widely investigated using different adsorbents. This study evaluated the significance of chitosan as a viable adsorbent for removing dyes from water treatment. We summarised the literature and research results obtained between 2009 and 2020 regarding the adsorption of dyes onto chitosan and modified chitosan-based adsorbents prepared through physical and chemical processing, including crosslinking impregnation, grafting, and membrane preparation. Furthermore, we demonstrated the effects of various chitosan-based materials and modifications; they all improve the properties of chitosan by promoting the adsorption of dyes. Hence, the application of chitosan-based materials with various modifications should be considered a cutting-edge approach for the remediation of dyes and other contaminants in aquatic environments toward the global aim of making potable water globally available.
Sustainable wastewater treatment is one of the biggest issues of the 21st century. Metals such as Zn2+ have been released into the environment due to rapid industrial development. In this study, dried watermelon rind (D-WMR) is used as a low-cost adsorption material to assess natural adsorbents' ability to remove Zn2+ from synthetic wastewater. D-WMR was characterized using scanning electron microscope (SEM) and X-ray fluorescence (XRF). According to the results of the analysis, the D-WMR has two colours, white and black, and a significant concentration of mesoporous silica (83.70%). Moreover, after three hours of contact time in a synthetic solution with 400 mg/L Zn2+ concentration at pH 8 and 30 to 40 °C, the highest adsorption capacity of Zn2+ onto 1.5 g D-WMR adsorbent dose with 150 μm particle size was 25 mg/g. The experimental equilibrium data of Zn2+ onto D-WMR was utilized to compare nonlinear and linear isotherm and kinetics models for parameter determination. The best models for fitting equilibrium data were nonlinear Langmuir and pseudo-second models with lower error functions. Consequently, the potential use of D-WMR as a natural adsorbent for Zn2+ removal was highlighted, and error analysis indicated that nonlinear models best explain the adsorption data.
The present work was aimed at evaluating the multi-metals column adsorption of lead(II), cadmium(II) and manganese(II) ions onto natural bentonite. The bentonite clay adsorbent was characterized for physical and chemical properties using X-ray diffraction, X-ray fluorescence, Brunauer-Emmett-Teller surface area and cation exchange capacity. The column performance was evaluated using adsorbent bed height of 5.0 cm, with varying influent concentrations (10 mg/L and 50 mg/L) and flow rates (1.4 mL/min and 2.4 mL/min). The result shows that the breakthrough time for all metal ions ranged from 50 to 480 minutes. The maximum adsorption capacity was obtained at initial concentration of 10 mg/L and flow rate of 1.4 mL/min, with 2.22 mg/g of lead(II), 1.71 mg/g of cadmium(II) and 0.37 mg/g of manganese(II). The order of metal ions removal by natural bentonite is lead(II) > cadmium(II) > manganese(II). The sorption performance and the dynamic behaviour of the column were predicted using Adams-Bohart, Thomas, and Yoon-Nelson models. The linear regression analysis demonstrated that the Thomas and Yoon-Nelson models fitted well with the column adsorption data for all metal ions. The natural bentonite was effective for the treatment of wastewater laden with multi-metals, and the process parameters obtained from this work can be used at the industrial scale.
Crosslinked chitosan beads were grafted with N-vinyl-2-pyrrolidone (NVP) using ammonium persulfate (APS) as free radical initiator. Important variables on graft copolymerization such as temperature, reaction time, concentration of initiator and concentration of monomer were optimized. The results revealed optimum conditions for maximum grafting of NVP on 1g crosslinked chitosan as follows: reaction temperature, 60°C; reaction time, 2h and concentrations of APS and NVP of 2.63×10-1M and 26.99×10-1M, respectively. The modified chitosan beads were characterized by FTIR spectroscopy, 13C NMR, SEM and BET to provide evidence of successful crosslinking and grafting reactions. The resulting material (cts(x)-g-PNVP) was evaluated as adsorbent for the removal of Cu(II) ions from aqueous solutions in a batch experiment. The Langmuir and Freundlich adsorption models were also applied to describe the equilibrium isotherms. The results showed that the adsorption of the copper ions onto the beads agreed well with Langmuir model with the maximum capacity (qmax) of 122mgg-1.
Chitosan ionic liquid beads were prepared from chitosan and 1-butyl-3-methylimidazolium based ionic liquids to remove Malachite Green (MG) from aqueous solutions. Batch adsorption experiments were carried out as a function of initial pH, adsorbent dosage, agitation time and initial MG concentration. The optimum conditions were obtained at pH 4.0, 0.008g of adsorbent dosage and 20min of agitation time were utilized in the kinetic and isotherm studies. Three kinetic models were applied to analyze the kinetic data and pseudo-second order was found to be the best fitted model with R2>0.999. In order to determine the adsorption capacity, the sorption data were analyzed using the linear form of Langmuir, Freundlich and Temkin equations. The isotherm was best fitted by Langmuir isotherm model. The maximum adsorption capacity (qmax) obtained from Langmuir isotherm for two chitosan beads 1-butyl-3-methylimidazolium acetate A and 1-butyl-3-methylimidazolium B are 8.07mgg-1 and 0.24mgg-1 respectively.
In the present study, iminodiacetic acid (IDA)-modified kenaf fiber, K-IDA formed by the chemical modification of plant kenaf biomass was tested for its efficacy as a sorbent material towards the purification of waste water. The K-IDA fiber was first characterized by the instrumental techniques like Fourier transform infrared (FTIR) analysis, elemental analysis (CHNSO), and scanning electron microscopy (SEM). On testing for the biosorption, we found that the K-IDA has an increment in the adsorption of Cu2+ ions as compared against the untreated fiber. The Cu2+ ions adsorption onto K-IDA fits very well with the Langmuir model and the adsorption maximum achieved to be 91.74mg/g. Further, the adsorption kinetics observed to be pseudo second-order kinetics model and the Cu2+ ions adsorption is a spontaneous endothermic process. The desorption study indicates a highest percentage of Cu2+ of 97.59% from K-IDA under 1M HCl solution against H2SO4 (72.59%) and HNO3 (68.66%). The reusability study indicates that the efficiency did not change much until the 4th cycle and also providing enough evidence for the engagement of our biodegradable K-IDA fiber towards the removal of Cu2+ ions in real-time waste water samples obtained from the electroplating and wood treatment industries.
Removal of low-concentration ammonia (1-10 ppm) from aquaculture wastewater was investigated via polysulfone (PSf)/zeolite mixed matrix membrane. PSf/zeolite mixed matrix membranes with different weight ratios (90/10, 80/20, 70/30 and 60/40 wt.%) were prepared and characterized. Results indicate that PSf/zeolite (80/20) was the most efficient membrane for removal of low-concentration ammonia. The ammonia elimination by PSf/zeolite (80/20) from aqueous solution for 10, 7, 5, 3 and 1 ppm of ammonia was 100%, 99%, 98.8%, 96% and 95% respectively. The recorded results revealed that pure water flux declined in higher loading of zeolite in the membrane matrix due to surface pore blockage caused by zeolite particles. On the other hand, ammonia elimination from water was decreased in higher contents of zeolite because of formation of cavities and macrovoids in the membrane substructure.
Dead calcareous skeletons (CSs) as low-cost adsorbents were studied to remove lead ions (Pb (II)) in an aqueous solution. Factors influencing the efficiency of CSs were evaluated by adsorbent size, contact time, initial concentration, dosage concentration and pH. The optimum CS size for removal of Pb (II) was 710 μm at an equilibrium time of 720 min. The best dosage of CS was 10 g/L for a 99% removal efficiency without pH adjustment. Pb (II) ions were effectively removed in the initial pH of the metal solution. CS was able to remove a high concentration (100 mg/L) of Pb (II) at a removal efficiency of 99.92% and at an adsorption capacity of 13.06 mg/g. Our results demonstrated the potential of CS as a metal adsorbent in the aqueous phase with a high-removal efficiency and distinct physical characteristics.
To develop a novel granular adsorbent to remove arsenic and antimony from water, calcined Mg/Al-layered double-hydroxide (CLDH)-incorporated polyethersulfone (PES) granular adsorbents (PES-LDH) were prepared using a core-shell method having 25% PES in an N,N-dimethylformamide solution. The PES-LDH displayed a spherical hollow shape having a rough surface and the average particle size of 1-2 mm. On the PES-LDH surface, nanosized CLDH (100-150 nm) was successfully immobilized by consolidation between PES and CLDH. The adsorption of Sb(V) by PES-LDH was found to be more favorable than for As(V), with the maximum adsorption capacity of As(V) and Sb(V) being 7.44 and 22.8 mg/g, respectively. The regeneration results indicated that a 0.5 M NaOH and 5 M NaCl mixed solution achieved an 80% regeneration efficiency in As(V) adsorption and desorption. However, the regeneration efficiency of Sb(V) gradually decreased due to its strong binding affinity, even though the PES-LDH showed much higher Sb(V) adsorption efficiency than As(V). This study suggested that PES-LDH could be a promising granular adsorbent for the remediation of As(V) and Sb(V) contained in wastewater.
The theme of present research demonstrates performance of copper (II) sulfate (CuSO4) as catalyst in thermolysis process to treat reactive black 5 (RB 5) dye. During thermolysis without presence of catalyst, heat was converted to thermal energy to break the enthalpy of chemical structure bonding and only 31.62% of color removal. With CuSO4 support as auxiliary agent, the thermally cleaved molecular structure was further destabilized and reacted with CuSO4. Copper ions functioned to delocalize the coordination of π of the lone paired electron in azo bond, C=C bond of the sp2 carbon to form C-C of the sp3 amorphous carbon in benzene and naphthalene. Further, the radicals of unpaired electrons were stabilized and RB 5 was thermally decomposed to methyl group. Zeta potential measurement was carried out to analyze the mechanism of RB 5 degradation and measurement at 0 mV verified the critical chemical concentration (CCC) (0.7 g/L copper (II) sulfate), as the maximum 92.30% color removal. The presence of copper (II) sulfate catalyst has remarkably increase the RB 5 dye degradation as the degradation rate constant without catalyst, k1 is 6.5224 whereas the degradation rate constant with catalyst, k2 is 25.6810. This revealed the correlation of conversion of thermal energy from heat to break the chemical bond strength, subsequent fragmentation of RB 5 dye molecular mediated by copper (II) sulfate catalyst. The novel framework on thermolysis degradation of molecular structure of RB 5 with respect to the bond enthalpy and interfacial intermediates decomposition with catalyst reaction were determined.
Phytoremediation has been applied as a promising and cost-effective technique for removing nutrient pollutants from wastewater. In this study, the effect of fullerene C60 was assessed on enhancing the phytoremediation efficiency of teak plants over a period of 1 month. Teak plants were supplied with fullerene C60 (0, 25, or 50 mg L-1) and fed daily with two types of urea plant wastewater (with and without adding optimum ratio of phosphorus and potassium). The required volume of wastewater by the teak plants, nitrogen removal percentage, plant growth parameters (plant height, number of leaves, leaf surface area, and dry biomass), and nutrient content was recorded throughout the study. The results showed that addition of 25 mg L-1 fullerene C60 to urea plant wastewater could increase water uptake and nitrogen recovery of the teak plants. Plant growth and nutrient contents of teak plants were also increased in the presence of 25 mg L-1 fullerene C60. However, addition of 50 mg L-1 fullerene C60 to the wastewater decreased the values for water uptake and nitrogen recovery. The findings indicated that addition of proper amount of fullerene C60 to the teak-based remediation system can increase the efficiency of the plants for nitrogen removal.
The present paper aims to assess the phytoremediation performance based on pollution removal efficiency of the highly polluted region of Alur Ilmu urban river for its applicability of on-site treatment. Thirteen stations along Alur Ilmu were selected to produce thematic maps through spatial distribution analysis based on six water quality parameters of Malaysia's Water Quality Index (WQI) for dry and raining seasons. The maps generated were used to identify the highly polluted region for phytoremediation applicability assessment. Four free-floating plants were tested in treating water samples from the highly polluted region under three different conditions, namely controlled, aerated and normal treatments. The selected free-floating plants were water hyacinth (Eichhornia crassipes), water lettuce (Pistia stratiotes), rose water lettuce (Pistia sp.) and pennywort (Centella asiatica). The results showed that Alur Ilmu was more polluted during dry season compared to raining season based on the water quality analysis. During dry season, four parameters were marked as polluted along Alur Ilmu, namely dissolve oxygen (DO), 4.72 mg/L (class III); ammoniacal nitrogen (NH3-N), 0.85 mg/L (class IV); total suspended solid (TSS), 402 mg/L (class V) and biological oxygen demand (BOD), 3.89 mg/L (class III), whereas, two parameters were classed as polluted during raining season, namely total suspended solid (TSS), 571 mg/L (class V) and biological oxygen demand (BOD), 4.01 mg/L (class III). The thematic maps generated from spatial distribution analysis using Kriging gridding method showed that the highly polluted region was recorded at station AL 5. Hence, water samples were taken from this station for pollution removal analysis. All the free-floating plants were able to reduce TSS and COD in less than 14 days. However, water hyacinth showed the least detrimental effect from the phytoremediation process compared to other free-floating plants, thus made it a suitable free-floating plants to be used for on-site treatment.
In this era of globalization, various products and technologies are being developed by the industries. While resources and energy are utilized from processes, wastes are being excreted through water streams, air, and ground. Without realizing it, environmental pollutions increase as the country develops. Effective technology is desired to create green factories that are able to overcome these issues. Wastewater is classified as the water coming from domestic or industrial sources. Wastewater treatment includes physical, chemical, and biological treatment processes. Aerobic and anaerobic processes are utilized in biological treatment approach. However, the current biological approaches emit greenhouse gases (GHGs), methane, and carbon dioxide that contribute to global warming. Microalgae can be the alternative to treating wastewater as it is able to consume nutrients from wastewater loading and fix CO2 as it undergoes photosynthesis. The utilization of microalgae in the system will directly reduce GHG emissions with low operating cost within a short period of time. The aim of this review is to discuss the uses of native microalgae species in palm oil mill effluent (POME) and flue gas remediation. In addition, the discussion on the optimal microalgae cultivation parameter selection is included as this is significant for effective microalgae-based treatment operations.
Massive utilization of bisphenol A (BPA) in the industrial production of polycarbonate plastics has led to the occurrence of this compound (at μg/L to ng/L level) in the water treatment plant. Nowadays, the presence of BPA in drinking water sources is a major concern among society because BPA is one of the endocrine disruption compounds (EDCs) that can cause hazard to human health even at extremely low concentration level. Parallel to these issues, membrane technology has emerged as the most feasible treatment process to eliminate this recalcitrant contaminant via physical separation mechanism. This paper reviews the occurrences and effects of BPA toward living organisms as well as the application of membrane technology for their removal in water treatment plant. The potential applications of using polymeric membranes for BPA removal are also discussed. Literature revealed that modifying membrane surface using blending approach is the simple yet effective method to improve membrane properties with respect to BPA removal without compromising water permeability. The regeneration process helps in maintaining the performances of membrane at desired level. The application of large-scale membrane process in treatment plant shows the feasibility of the technology for removing BPA and possible future prospect in water treatment process.
This study investigated the degradation pathway of metoprolol, a widely used β-blocker, in the ozonation via the identification of generated ozonation by-products (OPs). Structure elucidation of OPs was performed using HPLC coupled with quadrupole time-of-flight high-resolution mass spectrometry. Seven OPs were identified, and four of these have not been reported elsewhere. Identified OPs of metoprolol included aromatic ring breakdown by-products; aliphatic chain degraded by-products and aromatic ring mono-, di-, and tetrahydroxylated derivatives. Based on the detected OPs, metoprolol could be degraded through aromatic ring opening reaction via reaction with ozone (O3) and degradation of aliphatic chain and aromatic ring via reaction with hydroxyl radical (•OH).
Several parts of the world have been facing the problem of nitrite and nitrate contamination in ground and surface water. The acute toxicity of nitrite has been shown to be 10-fold higher than that of nitrate. In the present study, aminated silica carbon nanotube (ASCNT) was synthesised and tested for nitrite removal. The synergistic effects rendered by both amine and silica in ASCNT have significantly improved the nitrite removal efficiency. The IEP increased from 2.91 for pristine carbon nanotube (CNT) to 8.15 for ASCNT, and the surface area also increased from 178.86 to 548.21 m2 g-1. These properties have promoted ASCNT a novel adsorbent to remove nitrite. At optimum conditions of 700 ppm of nitrite concentration at pH 7 and 5 h of contact with 15 mg of adsorbent, the ASCNT achieved the maximal loading capacity of 396 mg/g (85% nitrite removal). The removal data of nitrite onto ASCNT fitted the Langmuir isotherm model better than the Freundlich isotherm model with the highest regression value of 0.98415, and also, the nonlinear analysis of kinetics data showed that the removal of nitrite followed pseudo-second-order kinetic. The positive values of both ΔS° and ΔH° suggested an endothermic reaction and an increase in randomness at the solid-liquid interface. The negative ΔG° values indicated a spontaneous adsorption process. The ASCNT was characterised using FESEM-EDX and FTIR, and the results obtained confirmed the removal of nitrite. Based on the findings, ASCNT can be considered as a novel and promising candidate for the removal of nitrite ions from wastewater.