The mineralisation of remazol black B (RBB) was studied at concentrations ranging from 20-1000 mgL(-1). The work was aimed at investigating the Fenton-like peroxidation of RBB at a concentration typically obtained in Batik cottage industries. Other response parameters were degradation and colour removal efficiencies. The parameters that were measured included total organic carbon (TOC), chemical oxygen demand (COD) as well as absorbance for mineralisation, degradation and colour. To optimise the process, the interaction effects of several controlling variables on the treatment process were examined using dispersion matrix-optimal design and response surface analysis. Four specific variables: initial dye concentration (Dye)o; the molar ratio of oxidant to dye organic strength (H2O2):(COD); the mass ratio of the oxidant to the catalyst (H2O2):(Fe3+) and reaction time (t(r)), were observed. Three reduced empirical models, one for each response, were developed for describing the treatment process. For 20, 510 and 1000 mgL(-1), the optimum %TOC reduction and oxidation times were 44% for 95 min, 52% for 52.5 min and 68% for 10 min corresponding to 67, 81 and 75% COD reduction, respectively. The optimum COD reduction and oxidation times were 89% for 95 min, 91% for 10 min and 84% for 95 min for concentrations of 20, 510 and 1000 mg L(-1), respectively. For all concentrations, total colour removal was achieved. A comparison of the results obtained in this study with literature values for traditional Fenton, photo-Fenton and photo-Fenton-like oxidation indicated that the TOC reduction obtained using the Fenton-like process was satisfactory.
Overgrowth of microalgae will result in harmful algae blooms that can affect the aquatic ecosystem and human health. Therefore, the quantitation of chlorophyll pigments can be used as an indicator of algae bloom. However, it is difficult to monitor the geographical and temporal distribution of chlorophyll in the aquatic environment. Accordingly, an innovative and inexpensive method based on the red-green-blue (RGB) image analysis was utilized in this study to estimate the microalgae chlorophyll content. The digital images were acquired using a smartphone camera. The colour index was then evaluated using software and associated with chlorophyll concentration significantly. A regression model, using RGB colour components as independent variables to estimate chlorophyll concentration, was developed and validated. The Green in the RGB index was the most promising way to estimate chlorophyll concentration in microalgae. The result showed that acetone was the best extractant solvent with a high R-squared value among the four extractant solvents. Next, the isolation of useful biomolecules, such as proteins, fatty acids, polysaccharides and antioxidants from the microalgae, has been recognized as an alternative to regulating algae bloom. Microalgae are shown to produce bioactive compounds with a variety of biological activities that can be applied in various industries. This study evaluates the biochemical composition of mixed microalgae species, Desmodesmus sp. and Scenedesmus sp. using the liquid triphasic partitioning (TPP) system. The findings from analytical assays revealed that the biomass consisted of varied concentrations of carbohydrates, protein, and lipids. Phenolic compounds and antioxidant activity were at 60.22 mg/L and 90.69%, respectively.
The objective of this research was to evaluate the treatment ofp-nitrophenol (PNP) as a sole organic carbon source using a sequencing batch reactor (SBR) with the addition of adsorbent. Two types of adsorbents, namely powdered activated carbon (PAC) and pyrolysed rice husk (PRH) were used in this study. Two identical SBRs, each with a working volume of 10 L, were operated with fill, react, settle, draw and idle periods in the ratio of 2:8:1:0.75:0.25 for a cycle time of 12 h. The results showed that, without the addition of adsorbent, increasing the influent PNP concentration to 200 mg/L resulted in the deterioration of chemical oxygen demand (COD) removal efficiency and PNP removal efficiency in the SBRs. Improvement in the performance of the SBR was observed with the addition of PAC. When the dosage of 1.0 g PAC/cycle was applied, COD removal of 95% and almost complete removal of PNP were achieved at the influent PNP concentration of 300 mg/L. The kinetic study showed that the rates of COD and PNP removal can be described by the first-order kinetics. The enhancement of performance in the PAC-supplemented SBR was postulated to be due to the initial adsorption of PNP by the freshly added and the bioregenerated PAC, thus reducing the inhibition on the microorganisms. The PRH was found to be ineffective because of its relatively low adsorption capacity for PNP, compared with that of PAC.
The objective of this study was to evaluate the effects ofNi(II) and Cr(VI) individually and in combination on the simultaneous removal of chemical oxygen demand (COD), nitrogen and metals under a sequencing batch reactor (SBR) operation. Three identical laboratory-scale SBRs were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in a ratio of 1:12:1:2:8 for a cycle time of 24 h until the steady state was achieved. Nickel(II) at increasing concentrations up to 35 mg/L was added to one of the reactors; Cr(VI) at increasing concentrations up to 25 mg/L was added to a second reactor; while a combination of Ni(II) and Cr(VI) in equal concentrations up to 10 mg/L was added to a third reactor. The results demonstrate that both Ni(II) and Cr(VI) exerted a more pronounced inhibitory effect on the removal of ammonia nitrogen (AN) than on COD removal. Synergistic and antagonistic inhibitory effects on the rates of COD and AN removal, respectively, were observed for the 50% Ni(II) and 50% Cr(VI) (w/w) mixture in the concentration range between 10 and 20 mg/L. The simultaneous presence of 50% Ni(II) and 50% Cr(VI) at a concentration of 20 mg/L resulted in system failure.
The efficiency of advanced oxidation processes (AOPs), enzymatic treatment and combined enzymatic/AOP sequences for the colour remediation of soda and chemimechanical pulp and paper mill effluent was investigated. The results indicated that under all circumstances, the AOP using ultraviolet irradiation (photo-Fenton) was more efficient in the degradation of effluent components in comparison with the dark reaction. It was found that both versatile peroxidase (VP) from Bjerkandera adusta and laccase from Trametes versicolor, as pure enzymes, decolorize the deep brown effluent to a clear light-yellow solution. In addition, it was found that in the laccase treatment, the decolorization rates of both effluents were enhanced in the presence of 2, 2'-azinobis (3-ethylbenzthiazoline-6-sulfonate), while in the case of VP, Mn(+2) decreased the efficiency of the decolorization treatment. The concomitant use of enzymes and AOPs imposes a considerable effect on the colour remediation of effluent samples.
A magnetic graphene oxide (MGO) was developed for the adsorption of As(III) from aqueous solution. The characteristics of MGO were investigated using Fourier-transform infrared (FTIR), X-ray diffraction and field emission scanning electron microscope-E/energy-dispersive X-ray analyses. Batch adsorption experiments were designed using central composite design, and the effects of adsorbent dosage, pH, contact time and concentration of As(III) were investigated. The MGO showed an excellent performance, removing up to 99.95% of As(III) under the following condition: initial As(III) concentration = 100 mg/L, pH = 7, adsorbent dosage = 0.3 g/L and contact time = 77 min. MGO dosage and initial pH were the most significant parameters influencing the process performance. FTIR analysis of the used adsorbent confirms the adsorption of As(III) through complexation between surface functional groups of the MGO and the oxyanions of As(III). The adsorbent maintained a significant level of performance even after four cycles of adsorption. Thus, the developed MGO has the potential to be used for the abatement of arsenic pollution.
Coating fertilizer particles with thin films is a possibility to control fertilizer release rates. It is observed that novel urea cross-linked starch-lignin composite thin films, prepared by solution casting, swell on coming into contact with water due to the increase in volume by water uptake by diffusion. The effect of lignin content, varied from 0% to 20% in steps of 5% at three different temperatures (25°C, 35°C and 45°C), on swelling of the film was investigated. By gravimetric analysis, the equilibrium water uptake and diffusion coefficient decrease with lignin content, indicating that the addition of lignin increases the hydrophobicity of the films. When temperature increases, the diffusion coefficient and the amount of water absorbed tend to increase. Assuming that swelling of the thin film is by water uptake by diffusion, the diffusion coefficient is estimated. The estimated diffusion coefficient decreases from 4.3 to 2.1 × 10-7 cm2/s at 25°C, from 5.3 to 2.9 × 10-7 cm2/s at 35°C and from 6.2 to 3.8 × 10-7 cm2/s at 45°C depending on the lignin content. Activation energy for the increase in diffusion coefficient with temperature is observed to be 16.55 kJ/mol. An empirical model of water uptake as a function of percentage of lignin and temperature was also developed based on Fick's law.
The sorption characteristics of Cr(VI) and Cu(II) by ethylenediamine modified rice hull from single and binary metal ion solutions were evaluated under various experimental conditions. Optimal Cr(VI) and Cu(II) removal from single metal ion solutions occurred at pH 2.0 and 5.5, respectively. Simultaneous removal of Cr(VI) and Cu(II) occurred at pH greater than 3.0. The sorption kinetics of Cr(VI) and Cu(II) from single and binary metal ion solutions were studied with reference to metal concentration, agitation rate and particle size. Sorption of Cr(VI) was more rapid than Cu(II). The kinetics of metal ion sorption fitted a pseudo-second order expression. The variation in the initial uptake rates was very small at an agitation rate beyond 150 rpm and sorption was generally independent of particle size. Equilibrium sorption data could be fitted into the Langmuir isotherm equation. Maximum sorption capacities of ethylenediamine modified rice hull for Cr(VI) at pH 2 and Cu(II) at pH 4 in single metal solutions were 0.45 and 0.06 mmol g(-1), respectively. This corresponds to an enhancement factor of 2.6 and 3 fold for Cr(VI) and Cu(II), respectively, compared to natural rice hull. A synergistic effect was observed for sorption of these ions in binary metal solutions.
Currently, an extractive green palm oil-based emulsion liquid membrane (ELM) has been used for simultaneous extraction and enrichment of Reactive Red 3BS from simulated synthetic dye wastewater. The ELM consists of two main phases, which are organic liquid membrane (LM) and stripping solution. During the extraction process, the ELM was dispersed into the simulated synthetic dye wastewater containing the Reactive Red 3BS complexes. The organic LM contains tridodecylamine (TDA), Sorbitan Monooleate (Span 80) and palm oil as a carrier, surfactant and diluent, respectively. The sodium bicarbonate (NaHCO3) was used as stripping solution for the enrichment process. Several important parameters that affected the simultaneous extraction and enrichment of Reactive Red 3BS, such as carrier and stripping agent concentrations, extraction time and treat ratio, were investigated. The results showed that almost 90% of Reactive Red 3BS ions were successfully extracted with 10 times enrichment in the stripping phase at the optimum conditions of 0.2 M TDA, 0.1 M NaHCO3, 5 min of extraction time and 1:5 of treat ratio. Hence, it can be concluded that palm oil possesses a high potential as green diluent in future technology, especially in ELM process for the removal and recovery of Reactive Red 3BS from synthetic dye wastewater.
Effluent containing colour/dyes, especially reactive dyes, becomes a great concern of wastewater treatment because it is toxic to human life and aquatic life. In this study, reactive dye of Black B was separated using the supported liquid membrane process. Commercial polypropylene membrane was used as a support of the kerosene-tridodecylamine liquid membrane. Several parameters were tested and the result showed that almost 100% of 70 ppm Black B was removed and 99% of 70 ppm Black B was recovered at pH 2 of the feed phase containing 0.00001 M Na2SiO3, flow rate of 150 ml/min and 0.2 M NaOH. The membrane support also remained stable for up to 36 hours under an optimum condition.
The potential of selected materials in treating metal-rich acid mine drainage (AMD) has been investigated in a series of batch experiment. The efficiencies of both single and mixed substrates under two conditions i.e. low- and high-concentration solutions containing heavy metals were evaluated. Synthetic metal-containing AMD was used in the experiments treated using spent mushroom compost (SMC), ochre, steel slag (SS), and limestone. Different ratios of treatment materials were incorporated in the substrate mix and were tested in an anoxic condition. In the batch test, physicochemical parameters (pH, redox potential, total dissolved solids, conductivity, and Ca concentration) and heavy metals (Fe, Mn, Pb, Zn, and Al) were analysed. The mixed substrates have shown satisfactory performance in increasing pH with increasing Ca concentration and removing metals. It has been found that SS and ochre played an important role in the treatment of AMD. The results showed that the mixed substrates SM1 (i.e. 10% SMC mixed with 20% ochre, 30% steel slag, and 40% limestone) and SM2 (i.e. 20% SMC mixed with 30% ochre, 40% steel slag, and 10% limestone) were effective in increasing the pH from as low as 3.5-8.09, and removing heavy metals with more than 90% removal efficiencies.
Landfills are one of the main point sources of groundwater pollution. This research mainly aims to assess the risk of nitrate [Formula: see text] transport from the unlined landfill to subsurface layers and groundwater using experimental results and the SESOIL model. Samples from 12 groundwater wells downstream of the landfill were collected and analyzed in 2008, 21 years after the landfill construction. The average [Formula: see text] concentration in the wells was 54 mg/L, slightly higher than the World Health Organization ([Formula: see text] 50 mg/L) standards. SESOIL model was used to predict the [Formula: see text] concentration at the bottom of the unsaturated zone. Results indicated that the current mean [Formula: see text] concentration at the bottom of the unsaturated zone is 75 mg/L. the model predicted that the level of NO3 will increased up to 325 mg/L within 30 years. Accordingly, the [Formula: see text] concentration in groundwater wells near the landfill area is expected to gradually increase with time. Although the current risk associated with the [Formula: see text] level might not be harm to adults, however, it might pose severe risks to both adults and infants in the near future due to [Formula: see text] leaching. Urgent mitigation measures such as final cell cover (cap), lining system and vertical expansion should be considered at the landfill to protect the public health in the area.
Microcystin-LR (MC-LR), which is one of the most commonly found microcystins (MCs) in fresh water, has been proved to be a potential tumour promoter and classified as 2B by the International Agency for Research on Cancer. MC-LR decomposition and inhibition of MC-LR production in Microcystis aeruginosa were investigated under electrolysis condition using an electrolysis cell consisting of Ti/Pt electrodes and Nafion membrane. The relationship between the decrease in MC-LR concentration and transcription of MC-LR synthesis gene clusters was determined by performing real-time reverse transcription polymerase chain reaction (RT-qPCR) to monitor changes in the levels of transcription encoding mcyB and mcyD (cDNA to DNA) in M. aeruginosa NIES 1086 under electrolysis condition and three different conditions (i.e. oxygenated, air aerated and unaerated) as controls. Cell density decreased from day 2 under electrolysis than under the three controls. Intracellular MC-LR concentration was approximately 33 fg cell-1 under electrolysis from days 4 to 8, while those in the other conditions ranged in 40-50 fg cell-1. The mcyB transcription continuously decreased from day 2 to nondetectable level in day 6 under electrolysis, while this transcription was stabilised under the three controls. This result suggested that oxidative stress, such as hydroxyl radicals, played an important role in the down-regulation of mcyB and mcyD gene transcription level and the MC-LR concentration and cell density of M. aeruginosa.
Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are the major polyfluoroalkyl substances (PFASs) contaminating global water environment. This study investigated the efficiency of granular activated carbon (GAC), ultrafiltration (UF) and nanofiltration (NF) treatment for removing PFOS and PFOA contaminants from lake water. NF gave greater removal of all contaminant types (in terms of organic matter, PFOS and PFOA) than GAC treatment which in turn was greater than UF treatment. The lower removal by UF was due to larger pore size of the membrane compared to the size of the target contaminants. For all treatment processes, lower pH (4) in the feedwater showed greater rejection of the organics and selected PFASs. This was likely due to increase in the electrostatic repulsion between solute and sorbent. It could be observed that on increasing the concentration of organics in the feed solution, the rejection of PFOA/PFOS decreased which was due to competition between organics and PFOS/PFOA for binding sites on the membrane/activated carbon surface. It was also noted that protein content led to greater influence for lower rejection of the PFOA/PFOS than carbohydrate or DOC content. This study demonstrated the potential use of membrane processes for removing emerging persistent organic pollutant removal from lake water.
Polyethersulphone (PES) membranes blended with silicon dioxide (SiO2) nanoparticles were prepared via a dry-jet wet spinning technique for the removal of bisphenol A (BPA) by adsorption mechanism. The morphology of SiO2 nanoparticles was analysed using a transmission electron microscopy and particle size distribution was also analysed. The prepared membranes were characterized by several techniques including field emission scanning electron microscopy, Fourier transform infrared spectroscopy and water contact angle. The adsorption mechanism of membrane towards BPA was evaluated by batch experiments and kinetic model. The influence of natural organic matter (NOM) in feed water on membrane BPA removal was also studied by filtration experiments. Results showed that BPA adsorption capacity as high as 53 µg/g could be achieved by the PES membrane incorporated with 2 wt% SiO2 in which the adsorption mechanism was in accordance with the pseudo-second-order kinetic model. The intraparticles diffusion model suggested that the rate limiting factor of membrane adsorption mechanism is governed by the diffusion of BPA into the membrane pores. The presence of 10 ppm NOM has reported to negatively reduce BPA removal by 24%, as it tended to compete with BPA for membrane adsorption. This work has demonstrated that PES-SiO2 membrane has the potential to eliminate trace amount of BPA from water source containing NOM.
Zeolites P in sodium (NaP) and potassium (KP) forms were used as adsorbents for the removal of calcium (Ca2+) and zinc (Zn2+) cations from aqueous solutions. Zeolite KP was prepared by ion exchange of K+ with Na+ which neutralizes the negative charge of the zeolite P framework structure. The ion exchange capacity of K+ on zeolite NaP was determined through the Freundlich isotherm equilibrium study. Characterization of zeolite KP was determined using infrared spectroscopy and X-ray diffraction (XRD) techniques. From the characterization, the structure of zeolite KP was found to remain stable after the ion exchange process. Zeolites KP and NaP were used for the removal of Ca and Zn from solution. The amount of Ca2+ and Zn2+ in aqueous solution before and after the adsorption by zeolites was analysed using the flame atomic absorption spectroscopy method. The removal of Ca2+ and Zn2+ followed the Freundlich isotherm rather than the Langmuir isotherm model. This result also revealed that zeolite KP adsorbs Ca2+ and Zn2+ more than zeolite NaP and proved that modification of zeolite NaP with potassium leads to an increase in the adsorption efficiency of the zeolite. Therefore, the zeolites NaP and KP can be used for water softening (Ca removal) and reducing water pollution/toxicity (Zn removal).
Start-up period is considered to be the most unstable and difficult stage in anaerobic process and usually takes a long time due to slow-degree adaptation of anaerobic microorganisms. In order to achieve a shorter start-up period, a novel modified anaerobic baffled reactor (MABR) has been developed in this study, where each modified baffle has its own characteristics (form/shape) to facilitate a treatment ofrecycled paper mill effluent (RPME). The results ofphysico-chemical characteristics showed that effluent from recycled paper mill consisted of 4328mgL-1 chemical oxygen demand (COD), 669mg L-1 biochemical oxygen demand and 501mg L-1 volatile fatty acid. It also consisted of variety of heavy metals such as zinc, magnesium, iron and nickel at concentrations of 1.39, 12.19, 2.39 and 0.72 mgL-1, respectively. Performance of MABR during the start-up period showed that methane production reached 34.7% with COD removal of 85% at steady state. The result indicates that MABR was successfully operated during the start-up period in treating RPME within a period of less than 30 days.
Pyrolysis of low density polyethylene (LDPE) waste from local waste separation company in subcritical water was conducted to investigate the effect of reaction time, temperature, as well as the mass ratio of water to polymer on the liquid yield. The data obtained from the study were used to optimize the liquid yield using response surface methodology. The range of reaction temperature used was 162-338°C, while the reaction time ranged from 37 min to 143 min, and the ratio of water to polymer ranged from 1.9 to 7.1. It was found that pyrolysis of LDPE waste in subcritical water produced hydrogen, methane, carbon monoxide and carbon dioxide, while the liquid product contained alkanes and alkenes with 10-50 carbons atoms, as well as heptadecanone, dichloroacetic acid and heptadecyl ester. The optimized conditions were 152.3°C, reaction time of 1.2 min and ratio of water solution to polymer of 32.7, with the optimum liquid yield of 13.6 wt% and gases yield of 2.6 wt%.
Biochar is a high-carbon-content organic compound that has potential applications in the field of energy storage and conversion. It can be produced from a variety of biomass feedstocks such as plant-based, animal-based, and municipal waste at different pyrolysis conditions. However, it is difficult to produce biochar on a large scale if the relationship between the type of biomass, operating conditions, and biochar properties is not understood well. Hence, the use of machine learning-based data analysis is necessary to find the relationship between biochar production parameters and feedstock properties with biochar energy properties. In this work, a rough set-based machine learning (RSML) approach has been applied to generate decision rules and classify biochar properties. The conditional attributes were biomass properties (volatile matter, fixed carbon, ash content, carbon, hydrogen, nitrogen, and oxygen) and pyrolysis conditions (operating temperature, heating rate residence time), while the decision attributes considered were yield, carbon content, and higher heating values. The rules generated were tested against a set of validation data and evaluated for their scientific coherency. Based on the decision rules generated, biomass with ash content of 11-14 wt%, volatile matter of 60-62 wt% and carbon content of 42-45.3 wt% can generate biochar with promising yield, carbon content and higher heating value via a pyrolysis process at an operating temperature of 425°C-475°C. This work provided the optimal biomass feedstock properties and pyrolysis conditions for biochar production with high mass and energy yield.
Petroleum sludge is a hazardous waste that contains various organic compounds including polycyclic aromatic hydrocarbons (PAHs) which have carcinogenic-mutagenic and toxic characteristics. This study focuses on the thermal treatment (indirect heating) of petroleum sludge cake for PAH degradation at 250, 450, and 650 degrees C using Ca(OH)2 + NaHCO3 as an additive. The treatment was conducted in a rotary drum electric heater. All experiments were carried out in triplicate. Concentrations of the 16 priority PAHs in gas (absorbed on Amberlite XAD-4 adsorbent), particulate (on quartz filter) and residue phases were determined using gas chromatography-mass spectrometry (GC-MS). The samples were extracted with acetonitrile by ultra-sonication prior to GC-MS analysis. The use of additive was beneficial and a temperature of 450 degrees C was suitable for PAH degradation. Low levels of PAH emissions, particularly carcinogenic PAH and toxic equivalent concentration (sigma TEC), were observed in gas, particulate and residue phases after treatment.