Chlorates are present in the brine stream purged from chlor-alkali plants. Tests were conducted using activated carbon from coconut shell, coal or palm kernel shell to adsorb chlorate. The results show varying levels of adsorption with reduction ranging between 1.3 g/L and 1.8 g/L. This was higher than the chlorate generation rate of that plant, recorded at 1.22 g/L, indicating that chlorate can be adequately removed by adsorption using activated carbon. Coconut based activated carbon exhibited the best adsorption of chlorate of the three types of activated carbon tested. Introducing an adsorption step prior to purging of the brine will be able to reduce chlorate content in the brine stream. The best location for introducing the adsorption step was identified to be after dechlorination of the brine and before resaturation. Introduction of such an adsorption step will enable complete recovery of the brine and prevent brine purging, which in turn will result in less release of chlorides and chlorates to the environment.
Unmetabolized pharmaceuticals often enter the water treatment plants and exposed to various treatment processes. Among these water treatment processes, disinfection is a process which involves the application of chemical oxidation to remove pathogen. Untreated pharmaceuticals from primary and secondary treatment have the potential to be exposed to the chemical oxidation process during disinfection. This study investigated the kinetics and mechanism of the degradation of sotalol during chlorination process. Chlorination with hypochlorous acid (HOCl) as main reactive oxidant has been known as one of the most commonly used disinfection methods. The second order rate constant for the reaction between sotalol and free available chlorine (FAC) was found to decrease from 60.1 to 39.1M-1min-1 when the pH was increased from 6 to 8. This result was mainly attributed by the decreased of HOCl concentration with increasing pH. In the real water samples, the presence of the higher amount of organic content was found to reduce the efficiency of chlorination in the removal of sotalol. This result showed that sotalol competes with natural organic matter to react with HOCl during chlorination. After 24h of FAC exposure, sotalol was found to produce three stable transformation by-products. These by-products are mainly chlorinated compounds. According to the acute and chronic toxicity calculated using ECOSAR computer program, the transformation by-products are more harmful than sotalol.
This work was aimed to evaluate the feasibility of castor bean residue based activated carbons prepared through metals chloride activation. The activated carbons were characterized for textural properties and surface chemistry, and the adsorption data of rhodamine B were established to investigate the removal performance. Zinc chloride-activated carbon with specific surface area of 395 m(2)/g displayed a higher adsorption capacity of 175 mg/g. Magnesium chloride and iron(III) chloride are less toxic and promising agents for composite chemical activation. The adsorption data obeyed Langmuir isotherm and pseudo-second-order kinetics model. The rate-limiting step in the adsorption of rhodamine B is film diffusion. The positive values of enthalpy and entropy indicate that the adsorption is endothermic and spontaneous at high temperature.
Penicillium simplicissimum (isolate 10), a metal tolerant fungus, tolerated 1000 mg/L Cu and 500 mg/L Zn, but were inhibited by Cd (100 mg/L), evident by the Tolerance Index (TI) of 0.88, 0.83, and 0.08, respectively. Live cells of P. simplicissimum were more effective in removing Cr (88.6%), Pb (73.7%), Cu (63.8%), Cd (33.1%), and Zn (28.3%) than dead cells (5.3-61.7%). Microscopy approach via SEM-EDX and TEM-EDX suggested that metal removal involved biosorption and bioaccumulation, with metal precipitates detected on the cell wall, and in the cytoplasm and vacuoles. FTIR analysis revealed metals interacted with amino, carbonyl, hydroxyl, phosphoryl (except Cd) and nitro groups in the cell wall. Biosorption and bioaccumulation of metals by live cells reduced Cu and Pb toxicity, observed from good root and (4.00-4.28 cm) and shoot (8.07-8.36 cm) growth of Vigna radiata in the phytotoxicity assay.
Nowadays, the pretreatment of wastewater prior to discharge is very important in various industries as the wastewater without any treatment contains high organic pollution loads that would pollute the receiving waterbody and potentially cause eutrophication and oxygen depletion to aquatic life. The reuse of seafood wastewater discharge in microalgae cultivation offers beneficial purposes such as reduced processing cost for wastewater treatment, replenishing ground water basin as well as financial savings for microalgae cultivation. In this paper, the cultivation of Chlorella vulgaris with an initial concentration of 0.01 ± 0.001 g⋅L-1 using seafood sewage discharge under sunlight and fluorescent illumination was investigated in laboratory-scale without adjusting mineral nutrients and pH. The ability of nutrient removal under different lighting conditions, the metabolism of C. vulgaris and new medium as well as the occurrence of auto-flocculation of microalgae biomass were evaluated for 14 days. The results showed that different illumination sources did not influence the microalgae growth, chemical oxygen demand (COD) and biochemical oxygen demand (BOD) significantly. However, the total nitrogen (total-N) and total phosphorus (total-P) contents of microalgae were sensitive to the illumination mode. The amount of COD, BOD, total-N and total-P were decreased by 88%, 81%, 95%, and 83% under sunlight mode and 81%, 74%, 79%, and 72% under fluorescent illumination, respectively. Furthermore, microalgae were auto-flocculated at the final days of cultivation with maximum biomass concentration of 0.49 ± 0.01 g⋅L-1, and the pH value had increased to pH 9.8 ± 0.1 under sunlight illumination.
An effective organoalkoxysilanes-grafted lignocellulosic waste biomass (OS-LWB) adsorbent aiming for high removal towards inorganic and organic mercury (Hg(II) and MeHg(II)) ions was prepared. Organoalkoxysilanes (OS) namely mercaptoproyltriethoxylsilane (MPTES), aminopropyltriethoxylsilane (APTES), aminoethylaminopropyltriethoxylsilane (AEPTES), bis(triethoxysilylpropyl) tetrasulfide (BTESPT), methacrylopropyltrimethoxylsilane (MPS) and ureidopropyltriethoxylsilane (URS) were grafted onto the LWB using the same conditions. The MPTES grafted lignocellulosic waste biomass (MPTES-LWB) showed the highest adsorption capacity towards both mercury ions. The adsorption behavior of inorganic and organic mercury ions (Hg(II) and MeHg(II)) in batch adsorption studies shows that it was independent with pH of the solutions and dependent on initial concentration, temperature and contact time. The maximum adsorption capacity of Hg(II) was greater than MeHg(II) which respectively followed the Temkin and Langmuir models. The kinetic data analysis showed that the adsorptions of Hg(II) and MeHg(II) onto MPTES-LWB were respectively controlled by the physical process of film diffusion and the chemical process of physisorption interactions. The overall mechanism of Hg(II) and MeHg(II) adsorption was a combination of diffusion and chemical interaction mechanisms. Regeneration results were very encouraging especially for the Hg(II); this therefore further demonstrated the potential application of organosilane-grafted lignocellulosic waste biomass as low-cost adsorbents for mercury removal process.
This study investigated the reaction kinetics and mechanism of the degradation of 5,5-diphenylhydantoin (DPH) during conventional chlorination and UV/chlorination. DPH is one of the antiepileptic drugs, which has frequently been detected in the aquatic environment. For chlorination, the second-order rate constant for the reaction between DPH and free active chlorine (FAC) was determined at pH 5 to 8. At pH 6 to 8, the efficiency of chlorination in the removal of DPH was found to be dominated by the reaction involving hypochlorous acid (HOCl). The result also showed that anionic species of DPH was more reactive toward FAC as compared with neutral DPH. For UV/chlorination, the effect of FAC dosage and pH on the degradation of DPH was evaluated. UV/chlorination is a more effective method for removing DPH as compared with conventional chlorination and UV irradiation. The DPH degradation rate was found to increase with increasing FAC concentration. On the other hand, the degradation of DPH was found to be more favorable under the acidic condition. Based on the identified transformation by-products, DPH was found to be degraded through the reaction at imidazolidine-2,4-dione moiety of DPH for both chlorination and UV/chlorination. Toxicity study on the chlorination and UV/chlorination-treated DPH solutions suggested that UV/chlorination is a more efficient method for reducing the toxicity of DPH.
Pristine chitosan beads were modified with sulfur (S)-containing functional groups to produce thiolated chitosan beads (ETB), thereby increasing S donor ligands and crosslinks. The effect of temperature, heating time, carbon disulfide (CS2)/chitosan ratio, and pH on total S content of ETB was examined using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The total S content of ETB increased with increasing CS2/chitosan ratio and decreased with decreasing pH and increasing temperature (>60 °C) and heating time (at 60 °C). Spectroscopic analyses revealed the presence of thiol (-SH)/thione, disulfide (-S-S-), and sulfonate groups in ETB. The thiolation mechanism involves decomposition of dithiocarbamate groups, thereby forming thiourea crosslinks and trithiocarbonate, resulting in -SH oxidation to produce -S-S- crosslinks. The partially formed ETB crosslinks contribute to its acid stability and are thermodynamically feasible in adsorbing Cd and Cu. The S-containing functional groups added to chitinous wastes act as sorbents for metal remediation from acidic environments.
Palm oil mill effluent (POME) is highly polluting wastewater generated from the palm oil milling process. Palm oil mill effluent was used as an electrolyte without any additive or pretreatment to perform electrocoagulation (EC) using electricity (direct current) ranging from 2 to 4 volts in the presence of aluminum electrodes with a reactor volume of 20 L. The production of hydrogen gas, removal of chemical oxygen demand (COD), and turbidity as a result of electrocoagulation of POME were determined. The results show that EC can reduce the COD and turbidity of POME by 57 and 62%, respectively, in addition to the 42% hydrogen production. Hydrogen production was also helpful to remove the lighter suspended solids toward the surface. The production of Al(OH)XHO at the aluminum electrode (anode) was responsible for the flocculation-coagulation process of suspended solids followed by sedimentation under gravity. The production of hydrogen gas from POME during EC was also compared with hydrogen gas production by electrolysis of tap water at pH 4 and tap water without pH adjustment under the same conditions. The main advantage of this study is to produce hydrogen gas while treating POME with EC to reduce COD and turbidity effectively.
A thermal degradation pathway of the decolourisation of Reactive Cibacron Blue F3GA (RCB) in aqueous solution through catalytic thermolysis is established. Catalytic thermolysis is suitable for the removal of dyes from wastewater as it breaks down the complex dye molecules instead of only transferring them into another phase. RCB is a reactive dye that consists of three main groups, namely anthraquinone, benzene and triazine groups. Through catalytic thermolysis, the bonds that hold the three groups together were effectively broken and at the same time, the complex molecules degraded to form simple molecules of lower molecular weight. The degradation pathway and products were characterized and determined through UV-Vis, FT-IR and GCMS analysis. RCB dye molecule was successfully broken down into simpler molecules, namely, benzene derivatives, amines and triazine. The addition of copper sulphate, CuSO4, as a catalyst, hastens the thermal degradation of RCB by aiding in the breakdown of large, complex molecules. At pH 2 and catalyst mass loading of 5 g/L, an optimum colour removal of 66.14% was observed. The degradation rate of RCB is well explained by first order kinetics model.
A recently reported stable and efficient EBPR system at high temperatures around 30 °C has led to characterization of kinetic and stoichiometric parameters of the Activated Sludge Model no. 2d (ASM2d). Firstly, suitable model parameters were selected by identifiability analysis. Next, the model was calibrated and validated. ASM2d was found to represent the processes well at 28 and 32 °C except in polyhyroxyalkanoate (PHA) accumulation of the latter. The values of the kinetic parameters for PHA storage (q PHA), polyphosphate storage (q PP) and growth (μ PAO) of polyphosphate-accumulating organisms (PAOs) at 28 and 32 °C were found to be much higher than those reported by previous studies. Besides, the value of the stoichiometric parameter for the requirement of polyphosphate for PHA storage (Y PO4) was found to decrease as temperature rose from 28 to 32 °C. Values of two other stoichiometric parameters, i.e. the growth yield of heterotrophic organisms (Y H) and PAOs (Y PAO), were high at both temperatures. These calibrated parameters imply that the extremely active PAOs of the study were able to store PHA, store polyphosphate and even utilize PHA for cell growth. Besides, the parameters do not follow the Arrhenius correlation due to the previously reported unique microbial clade at 28 and 32 °C, which actively performs EBPR at high temperatures.
The removal of toxic herbicide from wastewater is challenging due to the availability of suitable adsorbents. The Langsat empty fruit bunch is an agricultural waste and was used in this study as a cheap precursor to produce activated carbon for the adsorption of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) at different initial concentrations ranging from 50 to 400 mg/L. The produced Langsat empty fruit bunch activated carbon (LEFBAC) was mesoporous and had high surface area of 1065.65 m(2)/g with different active functional groups. The effect of shaking time, temperature and pH on 2,4-D removal were investigated using the batch technique. The adsorption capacity of 2,4-D by LEFBAC was decreased with increase in pH of solution whereas adsorption capacity increased with temperature. The adsorption data was well described by Langmuir isotherm followed by removal capacity of 261.2 mg/g at 30 °C. The results from this work showed that LEFBAC can be used as outstanding material for anionic herbicide uptake from wastewater.
The Malaysian palm oil industry is a major revenue earner and the country is ranked as one of the largest producers in the world. However, growth of the industry is synonymous with a massive production of agro-industrial wastewater. As an environmental protection and public health concern, the highly polluting palm oil mill effluent (POME) has become a major attention-grabber. Hence, the industry is targeting for POME pollution abatement in order to promote a greener image of palm oil and to achieve sustainability. At present, most palm oil mills have adopted the ponding system for treatment. Due to the successful POME pollution abatement experiences, Malaysia is currently planning to revise the effluent quality standards towards a more stringent discharge limits. Hence, the current trend of POME research focuses on developing tertiary treatment or polishing systems for better effluent management. Biotechnologically-advanced POME tertiary (polishing) technologies as well as other physicochemical methods are gaining much attention as these processes are the key players to push the industry towards the goal of environmental sustainability. There are still ongoing treatment technologies being researched and the outcomes maybe available in a while. However, the research completed so far are compiled herein and reported for the first time to acquire a better perspective and insight on the subject with a view of meeting the new standards. To this end, the most feasible technology could be the combination of advanced biological processes (bioreactor systems) with extended aeration, followed by solids separation prior to discharge. Chemical dosing is favoured only if effluent of higher quality is anticipated.
Simulation of fluidized bed reactor (FBR) was accomplished for treating wastewater using Fenton reaction, which is an advanced oxidation process (AOP). The simulation was performed to determine characteristics of FBR performance, concentration profile of the contaminants, and various prominent hydrodynamic properties (e.g., Reynolds number, velocity, and pressure) in the reactor. Simulation was implemented for 2.8 L working volume using hydrodynamic correlations, continuous equation, and simplified kinetic information for phenols degradation as a model. The simulation shows that, by using Fe(3+) and Fe(2+) mixtures as catalyst, TOC degradation up to 45% was achieved for contaminant range of 40-90 mg/L within 60 min. The concentration profiles and hydrodynamic characteristics were also generated. A subsequent scale-up study was also conducted using similitude method. The analysis shows that up to 10 L working volume, the models developed are applicable. The study proves that, using appropriate modeling and simulation, data can be predicted for designing and operating FBR for wastewater treatment.
This study evaluated the potential of bioflocculant production from Aspergillus niger using palm oil mill effluent (POME) as carbon source. The bioflocculant named PM-5 produced by A. niger showed a good flocculating capability and flocculating rate of 76.8% to kaolin suspension could be achieved at 60 h of culture time. Glutamic acid was the most favorable nitrogen source for A. niger in bioflocculant production at pH 6 and temperature 35 °C. The chemical composition of purified PM-5 was mainly carbohydrate and protein with 66.8% and 31.4%, respectively. Results showed the novel bioflocculant (PM-5) had high potential to treat river water from colloids and 63% of turbidity removal with the present of Ca(2+) ion.
Many industries discharge untreated wastewater into the environment. Heavy metals from many industrial processes end up as hazardous pollutants of wastewaters.Heavy metal pollution has increased in recent decades and there is a growing concern for the public health risk they may pose. To remove heavy metal ions from polluted waste streams, adsorption processes are among the most common and effective treatment methods. The adsorbents that are used to remove heavy metal ions from aqueous media have both advantages and disadvantages. Cost and effectiveness are two of the most prominent criteria for choosing adsorbents. Because cost is so important, great effort has been extended to study and find effective lower cost adsorbents.One class of adsorbents that is gaining considerable attention is agricultural wastes. Among many alternatives, palm oil biomasses have shown promise as effective adsorbents for removing heavy metals from wastewater. The palm oil industry has rapidly expanded in recent years, and a large amount of palm oil biomass is available. This biomass is a low-cost agricultural waste that exhibits, either in its raw form or after being processed, the potential for eliminating heavy metal ions from wastewater. In this article, we provide background information on oil palm biomass and describe studies that indicate its potential as an alternative adsorbent for removing heavy metal ions from wastewater. From having reviewed the cogent literature on this topic we are encouraged that low-cost oil-palm-related adsorbents have already demonstrated outstanding removal capabilities for various pollutants.Because cost is so important to those who choose to clean waste streams by using adsorbents, the use of cheap sources of unconventional adsorbents is increasingly being investigated. An adsorbent is considered to be inexpensive when it is readily available, is environmentally friendly, is cost-effective and be effectively used in economical processes. The advantages that oil palm biomass has includes the following:available and exists in abundance, appears to be effective technically, and can be integrated into existing processes. Despite these advantages, oil palm biomasses have disadvantages such as low adsorption capacity, increased COD, BOD and TOC. These disadvantages can be overcome by modifying the biomass either chemically or thermally. Such modification creates a charged surface and increases the heavy metal ion binding capacity of the adsorbent.
A two-staged engineered wetland-based system was designed and constructed to treat raw domestic septage. Hydraulic loading rates (HLRs) of 8.75 and 17.5 cm/d were studied with four and eight daily dosings at the second stage of the system to investigate the influence of the regimes on septage treatment. Removal of organic matter (OM) was found to be HLR dependent, where the results indicated that the increase of HLR from 8.75 to 17.5 cm/d impaired the overall level of treatment in the wetland units. Effluent of wetland fed at HLR 17.5 cm/d presented significantly lower oxygen reduction potential and dissolved oxygen values than wetland fed at 8.75 cm/d, indicative of the occurrence of less aerobic and reductive conditions in the bed. The reoxygenation capability of the wetland units was found to be heavily affected by the dosing frequency especially under high hydraulic load (17.5 cm/d). NH3-N degradation was found to decrease with statistical importance when the wetland was flushed two times more frequently with smaller batches of influent. The number of hydraulic load fractionings did not seem to affect the level of treatments of OM and ammonia for both the wetlands fed under the lower HLR of 8.75 cm/d. Prediction of hydraulic limits and management of the feeding strategies are important in the vertical type of engineered wetlands to guarantee the treatment performance and minimize the chances of filter clogging.
This paper reports on the direct ability of two positively charged organic polyelectrolytes (natural-based and synthetic) to reduce the atrazine concentration in water. The adsorption study was set up using multiple glass vessels with different polymer dosing levels followed by ultrafiltration with a 1 kDa membrane. The addition of polymers exhibited a capability in reducing the atrazine concentration up to a maximum of 60% in surface-to-volume ratio experiments. In the beginning, the theoretical L-type of the isotherm of Giles' classification was expected with an increase in the dosage of the polymer. However, in this study, the conventional type of isotherm was not observed. It was found that the adsorption of the cationic polymer on the negatively charged glass surface was necessary and influential for the removal of atrazine. Surface-to-volume ratio adsorption experiments were performed to elucidate the mechanisms and the polymer configuration. The glass surface area was determined to be a limiting parameter in the adsorption mechanism.
A greener method based on cloud point extraction was developed for removing phenol species including 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 4-nitrophenol (4-NP) in water samples by using the UV-Vis spectrophotometric method. The non-ionic surfactant DC193C was chosen as an extraction solvent due to its low water content in a surfactant rich phase and it is well-known as an environmentally-friendly solvent. The parameters affecting the extraction efficiency such as pH, temperature and incubation time, concentration of surfactant and salt, amount of surfactant and water content were evaluated and optimized. The proposed method was successfully applied for removing phenol species in real water samples.
Titania and ceria incorporated rice husk silica based catalyst was synthesized via sol-gel method using CTAB and glycerol as surface directing agents at room temperature and labeled as RHS-50Ti10Ce. The catalyst was used to study the adsorption and photodegradation of methylene blue (MB) under UV irradiation. The powder XRD pattern of RHS-50Ti10Ce was much broader (2θ=25-30°) than that of the parent RHS (2θ=22°). The catalyst exhibited type IV isotherm with H3 hysteresis loop, and the TEM images showed partially ordered pore arrangements. The TGA-DTG thermograms confirmed the complete removal of the templates after calcination at 500°C. RHS-50Ti10Ce exhibited excellent adsorption capability with more than 99% removal of MB from a 40 mg L(-1) solution in just 15 min. It also decolorized an 80 mg L(-1) MB solution under UV irradiation in 210 min, which was comparable with the commercialized pure anatase TiO2.