PAHs remediation from hazardous waste landfill leachate using fenton, photo - fenton and electro - fenton oxidation processes - performance evaluation under optimized conditions using RSM and ANN.

Polycyclic aromatic hydrocharbons (PAHs) are a class of highly toxic pollutants that are highly detrimental to the ecosystem. Landfill leechate emanated from municipal solid waste are reported to constitute significant PAHs. In the present investigation, three Fenton proceses, namely conventional Fenton, photo-fenton and electro-fenton methods have been employed to treat landfill leehcate for removing PAHs from a waste dumpig yard. Response surface methodology (RSM) and artificial neural network (ANN) methodologies were adopted to optimize and validate the conditions for optimum oxidative removal of COD and PAHs. The statistical analysis results showed that all independent variables chosen in the study are reported to have significant influence of the removal effects with P-values <0.05. Sensitivity analysis by the developed ANN model showed that the pH had the highest significance of 1.89 in PAH removal when compared to the other parameters. However for COD removal, H2O2 had the highest relative importance of 1.15, followed by Fe2+ and pH. Under optimal treatment conditions, the photo-fenton and electro-fenton processes showed better removal of COD and PAH compared to the Fenton process. The photo-fenton and electro-fenton treatment processes removed 85.32% and 74.64% of COD and 93.25% and 81.65% of PAHs, respectively. Also the investigations revelaed the presence of 16 distinct PAH compunds and the removal percentage of each of these PAHs are also reported. The PAH treatment research studies are generally limited to the assay of removal of PAH and COD levels. In the present investigation, in addition to the treatment of landfill leachate, particle size distribution analysis and elemental characterization of the resultant iron sludge by FESEM and EDX are reported. It was revealed that elemental oxygen is present in highest percentage, followed by iron, sulphur, sodium, chlorine, carbon and potassium. However, iron percentage can be reduced by treating the Fenton-treated sample with NaOH.

Adsorption of chromium, copper, lead and mercury ions from aqueous solution using bio and nano adsorbents: A review of recent trends in the application of AC, BC, nZVI and MXene.

Recent trends in adsorption of Chromium (Cr), Copper (Cu), Lead (Pb) and Mercury (Hg) in wastewater using (i) carbonaceous materials including activated carbon (AC) and biochar (BC), and (ii) nanomaterials including nano zero-valent iron (nZVI) and MXenes have been discussed in this paper. It has been found that adsorption capacity depends largely on the adsorbent modification technique, initial pH of wastewater, dosage of adsorbent, contact time and initial concentration of the pollutants. The pH value ranges for maximum removal of Cr, Cu, Pb and Hg have been reported as 2-4, 5-6, 5-8 and 3-8, respectively. Up to 99% removal of metals has been reported using AC, BC, nZVI and MXene. The mechanism involves the reduction and chemical adsorption of metals. AC and BC have a higher surface area (up to 5000 m2/g) compared to nZVI (up to 500 m2/g) and MXene (up to 67.66 m2/g). However, the higher reactivity and regeneration capacity of nZVI and MXene make them suitable adsorbents. From a practical point of view the application of adsorbents for real effluents, cost analysis, regeneration capability and reuse of heavy metals are some aspects that need attention in future studies. The removal efficiencies of AC and BC are comparable to the nZVI and MXene. The cost analysis may be an attractive aspect to decide the future application of these adsorbents at large scale.

Electrochemical oxidation of amoxicillin, ciprofloxacin and erythromycin in water: Effect of experimental factors on COD removal.

An alternative method of electrochemical oxidation was employed to degrade persistent compounds in the form of antibiotics using strong oxidizing agents such as hydroxyl ions. A 24 factorial design was employed to check the effect of four factors namely pH, current density, electrolysis time and electrolyte concentration set at their high (+) and low (-) levels on the antibiotics (amoxicillin, ciprofloxacin and erythromycin) degradation in water. The response was obtained in the form of COD (chemical oxygen demand) removal. A prediction model was developed to predict the values of COD removal. Later the main effect, contribution and interactions were studied with Design Expert Software 7.0. About 89.5% COD removal was obtained when pH and time were set at their high level and the other two factors at their low level. It was determined that the pH when set at high level (pH 9) had the most effect (24.68) and contribution (43.6) in the degradation process and hence the removal of COD. This technology of electrochemical oxidation can be employed in industries to efficiently remove pharmaceuticals, paints, dyes and other organic compounds.

Modeling of Cu(II) Adsorption from an Aqueous Solution Using an Artificial Neural Network (ANN).

This research optimized the adsorption performance of rice husk char (RHC4) for copper (Cu(II)) from an aqueous solution. Various physicochemical analyses such as Fourier transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (FESEM), carbon, hydrogen, nitrogen, and sulfur (CHNS) analysis, Brunauer-Emmett-Teller (BET) surface area analysis, bulk density (g/mL), ash content (%), pH, and pHZPC were performed to determine the characteristics of RHC4. The effects of operating variables such as the influences of aqueous pH, contact time, Cu(II) concentration, and doses of RHC4 on adsorption were studied. The maximum adsorption was achieved at 120 min of contact time, pH 6, and at 8 g/L of RHC4 dose. The prediction of percentage Cu(II) adsorption was investigated via an artificial neural network (ANN). The Fletcher-Reeves conjugate gradient backpropagation (BP) algorithm was the best fit among all of the tested algorithms (mean squared error (MSE) of 3.84 and R2 of 0.989). The pseudo-second-order kinetic model fitted well with the experimental data, thus indicating chemical adsorption. The intraparticle analysis showed that the adsorption process proceeded by boundary layer adsorption initially and by intraparticle diffusion at the later stage. The Langmuir and Freundlich isotherm models interpreted well the adsorption capacity and intensity. The thermodynamic parameters indicated that the adsorption of Cu(II) by RHC4 was spontaneous. The RHC4 adsorption capacity is comparable to other agricultural material-based adsorbents, making RHC4 competent for Cu(II) removal from wastewater.

Investigation of construction wastes generated in the Malaysian residential sector.

The construction sector is among the fastest growing sectors in Malaysia; it consumes a vast amount of natural resources and produces a massive volume of construction and demolition waste. The waste is collected in a decentralised manner by sub-contracted companies. It is challenging to obtain reliable information on the amount of construction waste generated, because it is hard to determine its exact quantity and composition. Therefore, this study proposes a quantitative construction waste estimation model for residential buildings according to available data collected from the Construction Industry Development Board, Malaysia. In the development of this model, a theoretical investigation of the construction procedure and the construction waste generation process was conducted. The waste generated rate was determined as 25.79 kg m-2 for new residential constructions, which translates into about 553,406 t of anticipated waste annually.

Enhancing the hydrophobicity of mangrove bark by esterification for oil adsorption.

Oil spills generally cause worldwide concern due to their detrimental effects on the environment and the economy. An assortment of commercial systems has been developed to control these spills, including the use of agricultural wastes as sorbents. This work deals with raw and modified mangrove barks (Rhizophora apiculata), an industrial lignocellulosic waste, as a low cost adsorbent for oil-product-spill cleanup in the aquatic environment. Mangrove bark was modified using fatty acids (oleic acid and palmitic acid) to improve its adsorption capacity. The oil sorption capacity of the modified bark was studied and compared with that of the raw bark. Kinetic tests were conducted with a series of contact times. The influence of particle size, oil dosage, pH and temperature on oil sorption capacity was investigated. The results showed that oleic acid treated bark has a higher sorption capacity (2,860.00 ± 2.00 mg/g) than untreated bark for Tapis crude oil. A correlation between surface functional groups, morphology and surface area of the adsorbent was studied by Fourier transform infrared spectrum, field emission scanning electron microscopy images and Brunauer-Emmett-Teller analysis. Isotherm study was conducted using the Langmuir and Freundlich isotherm models. The result showed that adsorption of crude oil on treated mangrove bark could be best described by the Langmuir model.

Remediation of carcinogenic PAHs from landfill leachate by Electro-Fenton process - Optimization and modeling.

PAHs is the group of emerging micro-pollutants present in most environmental matrices that has the tendency to bioaccumulate and cause carcinogenic effects to human health. The present research involved the quantification and treatment of leachate produced from secured landfill, to eliminate the PAHS. Electro-Fenton process, a class of advanced oxidation process, is adopted to degrade the PAHs using titanium electrodes as both anode and cathode. Artificial intelligence based statistical tool "Central Composite Design" a module of JMP -19 software was used to design the experiments and optimize the critical parameters involved in the research. It was observed that the value of P is significant (P < 0.05) for all the independent variables evidencing the significant correlation between experimental values and predicted values of the software. The value of R2 obtained was 0.96 and 0.97 for COD and PAHs respectively. The maximum removal efficiency of COD and PAH was found to be 84.24% and 90.78% respectively. The optimized conditions obtained from the central composite design were: pH = 5; Fe2+ = 0.1 g/L; H2O2 = 2 g/L; reaction time = 60 min; and electric intensity = 0.2 A. Additionally, optimized experimental conditions were used to study the removal efficiencies of individual 16 PAHs and are also reported. From the close proximity of experimental and predicted results of the software it can be proved that central composite design is efficient enough to be used as a statistical tool in design and analysis for treatment of landfill leachate.

Polycyclic aromatic hydrocarbon removal from petroleum sludge cake using thermal treatment with additives.

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.

Anaerobic treatment of ultrasound pretreated palm oil mill effluent (POME): microbial diversity and enhancement of biogas production.

In this study, palm oil mill effluent (POME) treated by ultrasonication at optimum conditions (sonication power: 0.88 W/mL, sonication duration: 16.2 min and total solids: 6% w/v) obtained from a previous study was anaerobically digested at different hydraulic retention times (HRTs). The reactor biomass was subjected to metagenomic study to investigate the impact on the anaerobic community dynamics. Experiments were conducted in two 5 L continuously stirred fill-and-draw reactors R1 and R2 operated at 30 ± 2 °C. Reactor R1 serving as control reactor was fed with unsonicated POME with HRT of 15 and 20 days (R1-15 and R1-20), whereas reactor R2 was fed with sonicated POME with the same HRTs (R2-15 and R2-20). The most distinct archaea community shift was observed among Methanosaeta (R1-15: 26.6%, R2-15: 34.4%) and Methanobacterium (R1-15: 7.4%, R2-15: 3.2%). The genus Methanosaeta was identified from all reactors with the highest abundance from the reactors R2. Mean daily biogas production was 6.79 L from R2-15 and 4.5 L from R1-15, with relative methane gas abundance of 85% and 73%, respectively. Knowledge of anaerobic community dynamics allows process optimization for maximum biogas production.

Multiple responses analysis and modeling of Fenton process for treatment of high strength landfill leachate.

Landfill leachate is one of the most recalcitrant wastes for biotreatment and can be considered a potential source of contamination to surface and groundwater ecosystems. In the present study, Fenton oxidation was employed for degradation of stabilized landfill leachate. Response surface methodology was applied to analyze, model and optimize the process parameters, i.e. pH and reaction time as well as the initial concentrations of hydrogen peroxide and ferrous ion. Analysis of variance showed that good coefficients of determination were obtained (R2 > 0.99), thus ensuring satisfactory agreement of the second-order regression model with the experimental data. The results indicated that, pH and its quadratic effects were the main factors influencing Fenton oxidation. Furthermore, antagonistic effects between pH and other variables were observed. The optimum H2O2 concentration, Fe(II) concentration, pH and reaction time were 0.033 mol/L, 0.011 mol/L, 3 and 145 min, respectively, with 58.3% COD, 79.0% color and 82.1% iron removals.

Strength enhancement of concrete using incinerated agricultural waste as supplementary cement materials.

The potassium (K) and sodium (Na) elements in banana are needed for hydration reaction that can enhance the strength properties of concrete. This research aims (a) to determine the material engineering properties of banana skin ash (BSA) and concrete containing BSA, (b) to measure the strength enhancement of concrete due to BSA, and (c) to identify optimal application of BSA as supplementary cement materials (SCM) in concrete. The BSA characterization were assessed through X-ray fluorescence (XRF) and Blaine's air permeability. The workability, compressive strength, and microstructures of concrete containing BSA were analysed using slump test, universal testing machine (UTM) and scanning electron microscope (SEM). A total of 15 oxides and 19 non-oxides elements were identified in BSA with K (43.1%) the highest and Na was not detected. At 20 g of mass, the BSA had a higher bulk density (198.43 ± 0.00 cm3) than ordinary Portland cement (OPC) (36.32 ± 0.00 cm3) indicating availability of large surface area for water absorption. The concrete workability was reduced with the presence of BSA (0% BSA: > 100 mm, 1% BSA: 19 ± 1.0 mm, 2%: 15 ± 0.0 mm, 3% BSA: 10 ± 0.0 mm). The compressive strength increased with the number of curing days. The concrete microstructures were improved; interfacial transition zones (ITZ) decreased with an increase of BSA. The optimal percentage of BSA obtained was at 1.25%. The established model showed significant model terms (Sum of Squares = 260.60, F value = 69.84) with probability of 0.01% for the F-value to occur due to noise. The established model is useful for application in construction industries.

Application of the central composite design for condition optimization for semi-aerobic landfill leachate treatment using electrochemical oxidation.

In the present study, Electrochemical Oxidation was used to remove COD and color from semi-aerobic landfill leachate collected from Pulau Burung Landfill Site (PBLS), Penang, Malaysia. Experiments were conducted in a batch laboratory-scale system in the presence of NaCl as electrolyte and aluminum electrodes. Central composite design (CCD) under Response surface methodology (RSM) was applied to optimize the electrochemical oxidation process conditions using chemical oxygen demand (COD) and color removals as responses, and the electrolyte concentrations, current density and reaction time as control factors. Analysis of variance (ANOVA) showed good coefficient of determination (R(2)) values of >0.98, thus ensuring satisfactory fitting of the second-order regression model with the experimental data. In un-optimized condition, maximum removals for COD (48.77%) and color (58.21%) were achieved at current density 80 mA/cm(2), electrolyte concentration 3,000 mg/L and reaction time 240 min. While after optimization at current density 75 mA/cm(2), electrolyte concentration 2,000 mg/L and reaction time 218 min a maximum of 49.33 and 59.24% removals were observed for COD and color respectively.

Influence of Fenton reagent oxidation on mineralization and decolorization of municipal landfill leachate.

This study evaluated the effectiveness of Fenton's technique for the treatment of semi-aerobic landfill leachate collected from Pulau Burung Landfill Site (PBLS), Penang, Malaysia. The Fe2+ or Fe3+ as catalyst and H2O2 as oxidizing agent are commonly used for the classical Fenton's reaction. In present study, the effect of operating conditions such as pH, reaction time, molar ratio, agitation rate, feeding mode and Fenton reagent concentrations which are important parameters that affect the removal efficiencies of Fenton method were investigated. Under the most favorable conditions, the highest removals of 58.1 and 78.3% were observed for COD and color, respectively. In general, the best operating conditions were pH = 3, Fe = 560 mg L(-1), H2O2 = 1020 mg L(-1), H2O2/Fe2+ molar ratio = 3, agitation rate = 400 rpm and reaction time = 120 minutes. The results highlighted that stepwise addition of Fenton's reagent was more effective than adding the entire volume in a single step. Excessive hydrogen peroxide and iron have shown scavenging effects on hydroxyl radicals and reduced degradation of refractory organics in the landfill leachate.

Ex-situ bioremediation of crude oil in soil, a comparative kinetic analysis.

Weathered crude oil (WCO) removals in shoreline sediment samples were monitored for 60 days in bioremediation experimentation. Experimental modeling was carried out using statistical design of experiments. At optimum conditions maximum of 83.13, 78.06 and 69.92% WCO removals were observed for 2, 16 and 30 g/kg initial oil concentrations, respectively. Significant variations in the crude oil degradation pattern were observed with respect to oil, nutrient and microorganism contents. Crude oil bioremediation were successfully described by a first-order kinetic model. The study indicated that the rate of hydrocarbon biodegradation increased with decrease of crude oil concentrations.

Effect of initial oil concentration and dispersant on crude oil biodegradation in contaminated seawater.

The effects of initial oil concentration and the Corexit 9500 dispersant on the rate of bioremediation of petroleum hydrocarbons were investigated with a series of ex-situ seawater samples. With initial oil concentrations of 100, 500, 1,000 and 2,000 mg/L, removal of total petroleum hydrocarbons (TPHs) with dispersant were 67.3%, 62.5%, 56.5% and 44.7%, respectively, and were 64.2%, 55.7%, 48.8% and 37.6% without dispersant. The results clearly indicate that the presence of dispersant enhanced crude oil biodegradation. Lower concentrations of crude oil demonstrated more efficient hydrocarbon removal. Based on these findings, bioremediation is not recommended for crude oil concentrations of 2,000 mg/L or higher.

Improved anaerobic digestion of palm oil mill effluent and biogas production by ultrasonication pretreatment.

Palm oil mill effluent (POME) is a highly polluted wastewater that consists of a high organic content of 4-5% total solids; a potential renewable energy source. A waste to energy study was conducted to improve biogas production using POME as substrate by ultrasonication pretreatment at mesophilic temperatures. The effect of temperature on the specific growth rate of anaerobes and methanogenic activity was investigated. Five sets of assays were carried out at operating temperatures between 25 °C and 45 °C. Each set consisted of two experiments using identical anaerobic sequencing batch reactors (AnSBR); fed with raw POME (control) and sonicated POME, respectively. The ultrasonication was set at 16.2 min ultrasonication time and 0.88 W mL-1 ultrasonication density with substrate total solids concentration of 6% (w/v). At 25 °C, biogas production rate and organic matter removal exhibited lowest values for both reactors. The maximum organic degradation was 96% from AnSBR operated at 30 °C fed with sonicated POME and 91% from AnSBR operated at 35 °C fed with unsonicated POME. In addition, the methane yield from AnSBR operated at 30 °C was enhanced by 21.5% after ultrasonication pretreatment. A few normality tests and a t-test were carried out. Both tests indicated that the residuals of the experimental data were normality distributed with mean equals to zero. The results demonstrated that ultrasonication treatment was a promising pretreatment to positively affect the organic degradation and biogas production rates at 30-35 °C.

Glycerol-Mediated Facile Synthesis of Colored Titania Nanoparticles for Visible Light Photodegradation of Phenolic Compounds.

In this study, we developed a glycerol-mediated safe and facile method to synthesize colored titania nanoparticles (NPs) via solution route. Our method is considerably effective and greener than other options currently available. Colored titania NPs were produced by hydrolyzing TiCl4 precursor in aqueous solution containing different concentrations of glycerol (0.0, 1.163, 3.834, and 5.815 mol/L) and subsequent calcination at 300 °C for 1 h. Our results highlight firstly that glycerol-mediated synthesis is unlikely to affect the anatase crystalline structure of TiO2, and secondly, that it would lead to coloration, band gap narrowing, and a remarkable bathochromic redshift of the optical response of titania. More importantly, the synthesized colored titania have Ti3+ ions, which, at least in terms of our samples, is the major factor responsible for its coloration. These Ti3+ species could induce mid gap states in the band gap, which significantly improve the visible light absorption capability and photocatalytic performance of the colored titania. The photocatalytic experiments showed that the colored TiO2 NPs prepared in 1.163 mol/L aqueous glycerol solution displayed the best photocatalytic performance. Almost 48.17% of phenolic compounds and 62.18% of color were removed from treated palm oil mill effluent (POME) within 180 min of visible light irradiation.

Removal of chromium (VI) from aqueous solution using treated oil palm fibre.

This study proposed an oil palm by-product as a low-cost adsorbent for the removal of hexavalent chromium [Cr (VI)] from aqueous solution. Adsorption of Cr (VI) by sulphuric acid and heat-treated oil palm fibre was conducted using batch tests. The influence of pH, contact time, initial chromium concentration and adsorbent dosage on the removal of Cr (VI) from the solutions was investigated. The optimum initial pH for maximum uptake of Cr (VI) from aqueous solution was found to be 1.5. The removal efficiency was found to correlate with the initial Cr (VI) concentration, adsorbent dosage as well as the contact time between Cr (VI) and the adsorbent. The adsorption kinetics tested with pseudo first order and pseudo second order models yielded high R(2) values from 0.9254 to 0.9870 and from 0.9936 to 0.9998, respectively. The analysis of variance (ANOVA) showed significant difference between the R(2) values of the two models at 99% confidence level. The Freundlich isotherm (R(2)=0.8778) described Cr (VI) adsorption slightly better than the Langmuir isotherm (R(2)=0.8715). Difficulty in desorption of Cr (VI) suggests the suitability of treated oil palm fibre as a single-use adsorbent for Cr (VI) removal from aqueous solution.

High surface area mesoporous activated carbon-alginate beads for efficient removal of methylene blue.

High surface area mesoporous activated carbon-alginate (AC-alginate) beads were successfully synthesized by entrapping activated carbon powder derived from Mangosteen fruit peel into calcium-alginate beads for methylene blue (MB) removal from aqueous solution. The structure and surface characteristics of AC-alginate beads were analyzed using Fourier transform infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and surface area analysis (SBET), while thermal properties were tested using thermogravimetric analysis (TGA). The effect of AC-alginate dose, pH of solution, contact time, initial concentration of MB solution and temperature on MB removal was elucidated. The results showed that the maximum adsorption capacity of 230mg/g was achieved for 100mg/L of MB solution at pH 9.5 and temperature 25°C. Furthermore, the adsorption of MB on AC-alginate beads followed well pseudo-second order equation and equilibrium adsorption data were better fitted by the Freundlich isotherm model. The findings reveal the feasibility of AC-alginate beads composite to be used as a potential and low cost adsorbent for removal of cationic dyes.

Powdered activated carbon augmented activated sludge process for treatment of semi-aerobic landfill leachate using response surface methodology.

This study was conducted to investigate aerobic biodegradation of semi-aerobic leachate with and without powdered activated carbon (PAC) addition. The experiment involved operating two 16L laboratory-scale activated sludge reactors in parallel at room temperature and adjusted to pH 6.5+/-0.5. One of the reactors was supplemented with PAC of 75-150microm size to observe its effect on semi-aerobic leachate biodegradation. Three hydraulic retention times (0.92, 1.57 and 2.22 d) and influent COD concentrations (750, 1800 and 2850mg/L) were applied in a factorial design for this study. The results showed enhanced reactor performance due to PAC addition with higher COD, colour and ammoniacal nitrogen removals. The PAC augmented reactor also had higher concentrations of NO(2)-N and NO(3)-N consequent of greater degree of nitrification.