This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).
This study investigated the reaction kinetics and degradation mechanism of parabens (methylparaben, ethylparaben, propylparaben and butylparaben) during ozonation. Experiments were performed at pH 2, 6 and 12 to determine the rate constants for the reaction of protonated, undissociated and dissociated paraben with ozone. The rate constants for the reaction of ozone with dissociated parabens (3.3 × 10(9)-4.2 × 10(9)M(-1)s(-1)) were found to be 10(4) times higher than the undissociated parabens (2.5 × 10(5)-4.4 × 10(5)M(-1)s(-1)) and 10(7) times higher than with the protonated parabens (1.02 × 10(2)-1.38 × 10(2)M(-1)s(-1)). The second-order rate constants for the reaction between parabens with hydroxyl radicals were found to vary from 6.8 × 10(9) to 9.2 × 10(9)M(-1)s(-1). Characterization of degradation by-products (DBPs) formed during the ozonation of each selected parabens has been carried out using GCMS after silylation. Twenty DBPs formed during ozonation of selected parabens have been identified. Hydroxylation has been found to be the major reaction for the formation of the identified DBPs. Through the hydroxylation reaction, a variety of hydroxylated parabens was formed.
This study was undertaken in order to understand the factors affecting the degradation of an insect repellent, N,N-diethyl-m-toluamide (DEET) by ozonation. Kinetic studies on DEET degradation were carried out under different operating conditions, such as varied ozone doses, pH values of solution, initial concentrations of DEET, and solution temperatures. The degradation of DEET by ozonation follows the pseudo-first-order kinetic model. The rate of DEET degradation increased exponentially with temperature in the range studied (20-50 degrees C) and in proportion with the dosage of ozone applied. The ozonation of DEET under different pH conditions in the presence of phosphate buffer occurred in two stages. During the first stage, the rate constant, k(obs), increased with increasing pH, whereas in the second stage, the rate constant, k(obs2), increased from pH 2.3 up to 9.9, however, it decreased when the pH value exceeded 9.9. In the case where buffers were not employed, the k(obs) were found to increase exponentially with pH from 2.5 to 9.2 and the ozonation was observed to occur in one stage. The rate of degradation decreased exponentially with the initial concentration of DEET. GC/MS analysis of the by-products from DEET degradation were identified to be N,N-diethyl-formamide, N,N-diethyl-4-methylpent-2-enamide, 4-methylhex-2-enedioic acid, N-ethyl-m-toluamide, N,N-diethyl-o-toluamide, N-acetyl-N-ethyl-m-toluamide, N-acetyl-N-ethyl-m-toluamide 2-(diethylamino)-1-m-tolylethanone and 2-(diethylcarbamoyl)-4-methylhex-2-enedioic acid. These by-products resulted from ozonation of the aliphatic chain as well as the aromatic ring of DEET during the degradation 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).
Marine algae have been reported as important sources of biogenic volatile halocarbons that are emitted into the atmosphere. These compounds are linked to destruction of the ozone layer, thus contributing to climate change. There may be mutual interactions between the halocarbon emission and the environment. In this study, the effect of irradiance on the emission of halocarbons from selected microalgae was investigated. Using controlled laboratory experiments, three tropical marine microalgae cultures, Synechococcus sp. UMACC 371 (cyanophyte), Parachlorella sp. UMACC 245 (chlorophyte) and Amphora sp. UMACC 370 (diatom) were exposed to irradiance of 0, 40 and 120 µmol photons m-2s-1. Stress in the microalgal cultures was indicated by the photosynthetic performance (Fv/Fm, maximum quantum yield). An increase in halocarbon emissions was observed at 120 µmol photons m-2s-1, together with a decrease in Fv/Fm. This was most evident in the release of CH3I by Amphora sp. Synechococcus sp. was observed to be the most affected by irradiance as shown by the increase in emissions of most halocarbons except for CHBr3 and CHBr2Cl. High positive correlation between Fv/Fm and halocarbon emission rates was observed in Synechococcus sp. for CH2Br2. No clear trends in correlation could be observed for the other halocarbons in the other two microalgal species. This suggests that other mechanisms like mitochondria respiration may contribute to halocarbon production, in addition to photosynthetic performance.
Lichen is a symbiotic organism that exists as a single composite body consisting of a mycobiont (fungus) and a photobiont (algae or a cyanobacterium). Many lichen species are considered as extremophiles due to their tolerance to radiation, desiccation, temperature and pollution. However, not all lichen species are tolerant to harsh environmental conditions as several species are sensitive for example to nitrogen, sulphur, acidity, heavy metals, halogens (e.g. fluoride) and ozone. Thus, to better understand why some lichens can withstand exposure to pollutants as opposed to those that are susceptible, we focused on the lichen species of Dirinaria known for their wide distribution in the tropics, subtropics and pantropical, and moderate tolerance to air pollution. Their moderate tolerance to air pollution affords them to thrive in good air quality environments as well as polluted air environments. Lichen samples of Dirinaria sp., UKM-J1 and UKM-K1, were respectively collected from two areas with different levels of air quality based on Air Pollutant Index or API (with index pollutant criteria of PM10, carbon monoxide, ozone, nitrogen dioxide and sulfur dioxide) in the outskirt of Jerantut (UKM-J1), a rural area in the middle of Peninsular Malaysia and the township of Klang (UKM-K1), in a busy area of the Klang Valley, Malaysia. API was monitored throughout 2012-2013 whereby the sample collection site in Klang showed markedly higher concentrations of pollutants in all the index pollutant criteria as compared to that of Jerantut. We performed transcriptome sequencing using Illumina RNA-seq technology and de novo assembly of the transcripts from the lichen samples. Raw reads from both libraries were deposited in the NCBI database with the accession number SRP138994.
The objective of this study was to investigate the performance of employing persulfate reagent in the advanced oxidation of ozone to treat stabilized landfill leachate in an ozone reactor. A central composite design (CCD) with response surface methodology (RSM) was applied to evaluate the relationships between operating variables, such as ozone and persulfate dosages, pH, and reaction time, to identify the optimum operating conditions. Quadratic models for the following four responses proved to be significant with very low probabilities (<0.0001): COD, color, NH3-N, and ozone consumption (OC). The obtained optimum conditions included a reaction time of 210 min, 30 g/m(3) ozone, 1g/1g COD0/S2O8(2-) ratio, and pH 10. The experimental results were corresponded well with predicted models (COD, color, and NH3-N removal rates of 72%, 96%, and 76%, respectively, and 0.60 (kg O3/kg COD OC). The results obtained in the stabilized leachate treatment were compared with those from other treatment processes, such as ozone only and persulfate S2O8(2-) only, to evaluate its effectiveness. The combined method (i.e., O3/S2O8(2-)) achieved higher removal efficiencies for COD, color, and NH3-N compared with other studied applications. Furthermore, the new method is more efficient than ozone/Fenton in advanced oxidation process in the treatment of the same studied leachate.
Time series analysis and forecasting has become a major tool in many applications in air pollution and environmental management fields. Among the most effective approaches for analyzing time series data is the model introduced by Box and Jenkins, ARIMA (Autoregressive Integrated Moving Average). In this study we used Box-Jenkins methodology to build ARIMA model for monthly ozone data taken from an Automatic Air Quality Monitoring System in Kemaman station for the period from 1996 to 2007 with a total of 144 readings. Parametric seasonally adjusted ARIMA (0,1,1) (1,1,2)12 model was successfully applied to predict the long-term trend of ozone concentration. The detection of a steady statistical significant upward trend for ozone concentration in Kemaman is quite alarming. This is likely due to sources of ozone precursors related to industrial activities from nearby areas and the increase in road traffic volume.
The use of rice husks (RH) to reinforce polymers in biocomposites are increasing tremendously. However, the incompatibility between the hydrophilic RH fibers and the hydrophobic thermoplastic matrices leads to unsatisfactory biocomposites. Surface modification of the fiber surface was carried out to improve the adhesion between fiber and matrix. In this study, the effect of surface modification of RH via alkali, acid and ultraviolet-ozonolysis (UV/O3) treatments on the properties of composites recycled high density polyethylene (rHDPE) composites was investigated. The untreated and treated RH were characterized by Fourier Transform Infrared (FTIR) and Scanning Electron Microscope (SEM). The composites containing 30 wt% of RH (treated and untreated) were then prepared via extrusion and followed by compression molding. As compared to untreated RH, all surface treated RH exhibited rougher surface and showed improved adhesion with rHDPE matrix. Tensile strength of UV/O3-treated RH composites showed an optimum result at 18.37 MPa which improved about 5% in comparison to the composites filled with untreated RH. UV/O3 treatment promotes shorter processing time and lesser raw material waste during treatment process where this is beneficial for commercialization in the future developments of wood plastic composites (WPCs). Therefore, UV/O3 treatment can be served as an alternative new method to modify RH surface in order to improve the adhesion between hydrophilic RH fibre and hydrophobic rHDPE polymer matrix.
Southeast Asian haze is a semi-natural phenomenon that chokes the region each year during the dry monsoon season. Smoke-haze episodes caused by the vegetation and peat fires in Indonesia severely affected large parts of Malaysia during the 2015 El Niño phenomenon. This study aimed to evaluate the factors that influenced the concentrations of aerosol and trace gases during the 2015 haze and non-haze period on a semi-urban site in the southern part of Malaysian peninsula that facing Sumatra (Muar, Site A), and on an urban site near to Kuala Lumpur, influenced by the city centre (Cheras, Site B). Local land use data and the cluster of air mass weighted backward trajectory were used to identify the potential factors from local sources and the transboundary region, respectively. The annual median concentrations of PM10 for semi-urban and urban sites were 45.0μg/m3 and 47.0μg/m3, respectively for the study period (Jan-Dec 2015) from the hourly observation dataset. The highest PM10 concentrations during the haze were 358μg/m3 and 415μg/m3 for the two sites, respectively, representing absolutely unhealthy air. However, the trace gases were within the safe threshold. The average concentrations of PM10 and carbon monoxide were two fold higher during the haze than the non-haze episodes on both sites. Nitrogen dioxide was more influenced by haze compared with sulphur dioxide and ozone. The results of the land use change suggest that the local factor can also partially affect the air pollution on the urban area (Site B) but more visible in 2015. The results of the backward trajectory and the wildfire radiative power showed that the smoke-haze episodes that affected Malaysia in 2015 were mainly initiated in the Indonesian Sumatra and Kalimantan regions. This study provides a very useful information towards the impacted region during El Niño haze episode.
Analysis and forecasting of air quality parameters are important topics of atmospheric and environmental research today due to the health impact caused by air pollution. This study examines transformation of nitrogen dioxide (NO(2)) into ozone (O(3)) at urban environment using time series plot. Data on the concentration of environmental pollutants and meteorological variables were employed to predict the concentration of O(3) in the atmosphere. Possibility of employing multiple linear regression models as a tool for prediction of O(3) concentration was tested. Results indicated that the presence of NO(2) and sunshine influence the concentration of O(3) in Malaysia. The influence of the previous hour ozone on the next hour concentrations was also demonstrated.
Landfill leachate can threaten the environment and human life. Therefore, this study aims to investigate the efficiency of ozone (O3 ), O3 with zirconium tetrachloride (O3 /ZrCl4 ), and O3 with tin tetrachloride (O3 /SnCl4 ) in remediating the stabilized anaerobic landfill leachate (SAL) from Alor Pongsu, Perak. Hydroxyl radical (OH•) is an important oxidizing agent in the ozonation process. Its presence was tested using tert-butyl alcohol. Results showed that using ZrCl4 and SnCl4 in ozonation boosted the generation of hydroxyl radical, thereby enhancing the oxidation process and pollutant removal inside the sample. The O3 /ZrCl4 mix at chemical oxygen demand (COD) to ZrCl4 ratio of 1:1.5, pH 8-9, and 90-min reaction time resulted in the highest reduction rates of COD and color at 91.9% and 99.6%, respectively. All results demonstrated that the optimum performance occurred at alkaline conditions (pH > 8), proving that OH radicals primarily oxidized the pollutants through an indirect reaction pathway. The biodegradability (biochemical oxygen demand/COD) ratio was also considerably improved from 0.02 (raw) to 0.37 using O3 /ZrCl4 , compared with using O3 alone and using O3 /SnCl4 , which only recorded 0.23 and 0.28, respectively, after the treatment. The study demonstrated that O3 /ZrCl4 was the most efficient combination. PRACTITIONER POINTS: The O3 /ZrCl4 recorded the highest COD and color removals. The O3 /ZrCl4 combination also recorded higher OH• concentrations. The biodegradability of leachate (BOD5 /COD ratio) improved from 0.02 to 0.37.
Acetaminophen (Ace) is a trace pollutant widely found in sewage treatment plant (STP) wastewater. We test the feasibility of coconut shell waste, a low cost adsorbent from coconut industry, for removing Ace from synthetic solution in a fixed-bed column adsorption. To enhance its performance, the surface of granular activated carbon (GAC) was pre-treated with NaOH, HNO3, ozone, and/or chitosan respectively. The results show that the chemical modification of the GAC's surface with various chemicals has enhanced its Ace removal during the column operations. Among the modified adsorbents, the ozone-treated GAC stands out for the highest Ace adsorption capacity (38.2 mg/g) under the following conditions: 40 mg/L of Ace concentration, 2 mL/min of flow rate, 45 cm of bed depth. Both the Thomas and the Yoon-Nelson models are applicable to simulate the experimental results of the column operations with their adsorption capacities: ozone-treated GAC (20.88 mg/g) > chitosan-coated GAC (16.67 mg/g) > HNO3-treated GAC (11.09 mg/g) > NaOH-treated GAC (7.57 mg/g) > as-received GAC (2.84 mg/g). This suggests that the ozone-treated GAC is promising and suitable for Ace removal in a fixed-bed reactor.
In recent years, Malaysia has experienced quite a few number of chronic air pollution problems and it has become a
major contributor to the deterioration of human health and ecosystems. This study aimed to assess the air quality data
and identify the pattern of air pollution sources using chemometric analysis through hierarchical cluster analysis (HCA),
discriminant analysis (DA), principal component analysis (PCA) and multiple linear regression analysis (MLR). The air
quality data from January 2016 until December 2016 was obtained from the Department of Environment Malaysia. Air
quality data from eight sampling stations in Selangor include the selected variables of nitrogen dioxide (NO2
), ozone (O3
),
sulfur dioxide (SO2
), carbon monoxide (CO) and particulate matter (PM10). The HCA resulted in three clusters, namely low
pollution source (LPS), moderate pollution source (MPS) and slightly high pollution source (SHPS). Meanwhile, DA resulted
in two and four variables for the forward stepwise mode and the backward stepwise mode, respectively. Through PCA,
it was identified that the main pollutants of LPS, MPS and SHPS came from industrial and vehicle emissions, agricultural
systems, residential factors and natural emission sources. Among the three models yielded from the MLR analysis, it was
found that SHPS is the most suitable model to be used for the prediction of Air Pollution Index. This study concluded that
a clearer review and practical design of air quality monitoring network would be beneficial for better management of
air pollution. The study also suggested that chemometric techniques have the ability to show significant information on
spatial variability for large and complex air quality data.
Frequent haze occurrences in Malaysia have made the management of PM10 (particulate matter with aerodynamic less than 10 μm) pollution a critical task. This requires knowledge on factors associating with PM10 variation and good forecast of PM10 concentrations. Hence, this paper demonstrates the prediction of 1-day-ahead daily average PM10 concentrations based on predictor variables including meteorological parameters and gaseous pollutants. Three different models were built. They were multiple linear regression (MLR) model with lagged predictor variables (MLR1), MLR model with lagged predictor variables and PM10 concentrations (MLR2) and regression with time series error (RTSE) model. The findings revealed that humidity, temperature, wind speed, wind direction, carbon monoxide and ozone were the main factors explaining the PM10 variation in Peninsular Malaysia. Comparison among the three models showed that MLR2 model was on a same level with RTSE model in terms of forecasting accuracy, while MLR1 model was the worst.
Ozonation, combined with the Fenton process (O(3)/H(2)O(2)/Fe(2+)), was used to treat matured landfill leachate. The effectiveness of the Fenton molar ratio, Fenton concentration, pH variance, and reaction time were evaluated under optimum operational conditions. The optimum removal values of chemical oxygen demand (COD), color, and NH(3)-N were found to be 65%, 98%, and 12%, respectively, for 90 min of ozonation using a Fenton molar ratio of 1 at a Fenton concentration of 0.05 mol L(-1) (1700 mg/L) H(2)O(2) and 0.05 mol L(-1) (2800 mg/L) Fe(2+) at pH 7. The maximum removal of NH(3)-N was 19% at 150 min. The ozone consumption for COD removal was 0.63 kg O(3)/kg COD. To evaluate the effectiveness, the results obtained in the treatment of stabilized leachate were compared with those obtained from other treatment processes, such as ozone alone, Fenton reaction alone, as well as combined Fenton and ozone. The combined method (i.e., O(3)/H(2)O(2)/Fe(2+)) achieved higher removal efficiencies for COD, color, and NH(3)-N compared with other studied applications.
The objective of this study was to investigate the performance of employing Fenton's reagent in the advanced oxidation of ozone to treat stabilized landfill leachate in an ozone reactor. A central composite design (CCD) with response surface methodology (RSM) was applied to evaluate the relationships between operating variables, such as ozone and Fenton dosage, pH, and reaction time, to identify the optimum operating conditions. Quadratic models for the following four responses proved to be significant with very low probabilities (<0.0001): chemical oxygen demand (COD), color, NH-N, and ozone consumption (OC). The obtained optimum conditions included a reaction time of 90 min, 30 g/m³ ozone, 0.01 mol/L₂H₂O,0.02 mol/L Fe²⁺, and pH 5. COD, color, and NH₃-N removal rates of 79%, 100%, and 20%, respectively, and 0.18 kg O₃/kg COD OC were obtained. The predictions correspond well with experimental results (COD, color, and NH-N removal rates of 78%, 98.5%, and 19%, respectively, and 0.29 kg O₃/kg COD OC). This method reduces the treatment time and improves the treatment efficiency relative to a previously published method that used Fenton's reagent prior to ozonation.
The usage of ozone in dentistry has been proposed because of its antimicrobial, disinfectant, biocompatibility and healing properties. In the last decade a number of therapeutic protocols with ozone have been developed to address common dental infections associated with periodontal disease, RCT and caries. Despite these advantages, therapeutic ozone's application in dentistry is limited because of its possible side effects. Hence, dental practitioners need to know the proper usage of ozone therapy that can provide better patient care and considerably cut down the time and cost of the treatment.
Membrane bioreactor (MBR) is regarded as the state-of-the-art technology in separation processes. Surface modification techniques play a critical role in improving the conventional membrane system which is mostly hydrophobic in nature. The hydrophobic nature of membranes is known to cause fouling, resulting in high maintenance costs and shorter lifespan of MBR. Thus, surface grafting aims to improve the hydrophilicity of bio-based membrane systems. This review describes the major surface grafting techniques currently used in membranes, including photo induced grafting, plasma treatment and plasma induced grafting, radiation induced grafting, thermal induced grafting and ozone induced grafting. The advantages and disadvantages of each method is discussed along with their parametric studies. The potential applications of MBR are very promising, but some integral membrane properties could be a major challenge that hinders its wider reach. The fouling issue could be resolved with the surface grafting techniques to achieve better performance of MBRs.