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 novel and economic sequential process consisting of precipitation, adsorption, and oxidation was developed to remediate actual rare-earth (RE) wastewater containing various toxic pollutants, including radioactive species. In the precipitation step, porous air stones (PAS) containing waste oyster shell (WOS), PASWOS, was prepared and used to precipitate most heavy metals with >97% removal efficiencies. The SEM-EDS analysis revealed that PAS plays a key role in preventing the surface coating of precipitants on the surface of WOS and in releasing the dissolved species of WOS successively. For the adsorption step, a polyurethane (PU) impregnated by coal mine drainage sludge (CMDS), PUCMDS, was synthesized and applied to deplete fluoride (F), arsenic (As), uranium (U), and thorium (Th) that remained after precipitation. The continuous-mode sequential process using PAS(WOS), PU(CMDS), and ozone (O3) had 99.9-100% removal efficiencies of heavy metals, 99.3-99.9% of F and As, 95.8-99.4% of U and Th, and 92.4% of COD(Cr) for 100 days. The sequential process can treat RE wastewater economically and effectively without stirred-tank reactors, pH controller, continuous injection of chemicals, and significant sludge generation, as well as the quality of the outlet met the EPA recommended limits.
Microcystins-LR (MC-LR) which is a kind of potent hepatotoxin for humans and wildlife can be biodegraded by microbial community. In this study, the capacity of biofilm in degrading MC-LR was investigated with and without additional metal ions (Mn(2+), Zn(2+) and Cu(2+)) at the concentration of 1 mg L(-1). The results indicated that the degradation rate of MC-LR by biofilm was inhibited by introduced Mn(2+) and Cu(2+) during the whole culture period. MC-LR cannot be degraded until a period of culture time passed both in the cases with Zn(2+) and Cu(2+) (2 and 8 days for Zn(2+) and Cu(2+), respectively). The results of mlrA gene analysis showed that the abundance of MC-LR degradation bacteria (MCLDB) in the microbial community under Mn(2+) condition was generally lower than that under no additional metal ion condition. Meanwhile, a two days lag phase for the proliferation of MCLDB occurred after introducing Zn(2+). And a dynamic change of MCLDB from Cu(2+) inhibited species to Cu(2+) promoted species was observed under Cu(2+) condition. The maximum ratio of MCLDB to overall bacteria under various conditions during culture process was found to follow the tendency as: Cu(2+) > Zn(2+) ≈ no additional metal ion (Control) > Mn(2+), suggesting the adverse effect of Mn(2+), no obvious effect of Zn(2+) and positive effect of Cu(2+) on the distribution ratio of MCLDB over the biofilm.
We evaluated the potential for biomagnification of endocrine disrupting chemicals (EDCs) such as nonylphenol (NP), octylphenol (OP), bisphenol A (BP), and natural estrogens such as estrone (E1) and 17β-estradiol (E2) in a benthic fish, Pleuronectes yokohamae. The assimilation efficiencies (AE) of most EDCs ranged from 88 to 96% suggesting that they were efficiently incorporated and assimilated into P. yokohamae, except for NP (50%). However, the biomagnification factor (BMF) values were <1.0 suggesting that the compounds were not biomagnifying. Additionally, three of the target EDCs were not detected (BP, E1 and E2). Glucuronidation activity towards BP (11.44 ± 2.5 nmol/mg protein/min) and E2 (12.41 ± 3.2 nmol/mg protein/min) was high in the intestine suggesting that EDCs were glucuronidated prior to excretion into bile. Thus, we conclude that biomagnification of dietary EDCs is reduced in P. yokohamae because of effective glucuronidation.
This study was carried out to evaluate the efficiency of Guar gum in removing Persistent Organic Pollutants (POPs), viz. phenol,2,4-bis(1,1-dimethylethyl) and bis(2-ethylhexyl) phthalate (DEHP), from farm effluent. The removal efficiency was compared with alum. The results indicated that 4.0 mg L(-1) of Guar gum at pH 7 could remove 99.70% and 99.99% of phenol,2,4-bis(1,1-dimethylethyl) and DEHP, respectively. Box Behnken design was used for optimization of the operating parameters for optimal POPs removal. Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) spectroscopy studies were conducted on the flocs. SEM micrographs showed numerous void spaces in the flocs produced by Guar gum as opposed to those produced by alum. This indicated why Guar gum was more effective in capturing and removal of suspended particles and POPs as compared to alum. FTIR spectra indicated a shift in the bonding of functional groups in the flocs produced by Guar gum as compared to raw Guar gum powder signifying chemical attachment of the organics present in the effluent to the coagulant resulting in their removal. Guar gum is highly recommended as a substitute to chemical coagulant in treating POPs due to its non-toxic and biodegradable characteristics.
Samples of mangrove snails Nerita lineata and surface sediments were collected from nine geographical sampling sites in Peninsular Malaysia to determine the concentrations of eight metals. For the soft tissues, the ranges of metal concentrations (μg g(-1) dry weight (dw)) were 3.49-9.02 for As, 0.69-6.25 for Cd, 6.33-25.82 for Cu, 0.71-6.53 for Cr, 221-1285 for Fe, 1.03-50.47 for Pb, and 102.7-130.7 for Zn while Hg as 4.00-64.0 μg kg(-1) dw(-1). For sediments, the ranges were 21.81-59.49 for As, 1.11-2.00 for Cd, 5.59-28.71 for Cu, 18.93-62.91 for Cr, 12973-48916 for Fe, 25.36-172.57 for Pb, and 29.35-130.34 for Zn while for Hg as 2.66-312 μg kg(-1) dw(-1). To determine the ecological risks on the surface habitat sediments, sediment quality guidelines (SQGs), the geochemical indices, and potential ecological risk index (PERI) were used. Based on the SQGs, all the metals investigated were most unlikely to cause any adverse effects. Based on geoaccumulation index and enrichment factor, the sediments were also not polluted by the studied metals. The PERI values based on As, Cd, Cu, Cr, Hg, Pb and Zn in this study were found as 'low ecological risk'. In order to assess the potential health risks, the estimated daily intakes (EDI) of snails were found to be all lower than the RfD guidelines for all metals, except for Pb in some sites investigated. Furthermore, the calculated target hazard quotients (THQ) were found to be less than 1. However, the calculated total target hazard quotients (TTHQ) from all sites were found to be more than 1 for high level consumers except KPPuteh. Therefore, moderate amount of intake is advisable to avoid human health risks to the consumers.
The impact of ionic strength (from 0.003 to 500mM) and salt type (NaCl vs MgCl2) on transport and retention of titanium dioxide (TiO2) nanoparticles (NPs) in saturated limestone porous media was systematically studied. Vertical columns were packed with limestone grains. The NPs were introduced as a pulse suspended in aqueous solutions and breakthrough curves in the column outlet were generated using an ultraviolent-visible spectrometry. Presence of NaCl and MgCl2 in the suspensions were found to have a significant influence on the electrokinetic properties of the NP aggregates and limestone grains. In NaCl and MgCl2 solutions, the deposition rates of the TiO2-NP aggregates were enhanced with the increase in ionic strength, a trend consistent with traditional Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Furthermore, the NP aggregates retention increased in the porous media with ionic strength. The presence of salts also caused a considerable delay in the NPs breakthrough time. MgCl2 as compared to NaCl was found to be more effective agent for the deposition and retention of TiO2-NPs. The experimental results followed closely the general trends predicted by the filtration and DLVO calculations. Overall, it was found that TiO2-NP mobility in the limestone porous media depends on ionic strength and salt type.
The Changbai (also known as "Baekdu") Mountain, on the border between China and North Korea, is the highest mountain (2750 m) in northeastern China. Recently, this mountain region has experienced a dramatic increase in air pollution, not only because of increasing volumes of tourism-derived traffic but also because of the long-range transport of polluted westerly winds passing through major industrial and urban cities in the eastern region of China. To assess the relative importance of the two sources of pollution, 16 polycyclic aromatic hydrocarbons (PAHs) as model substances were determined in the mountain soil. A total of 32 soil samples were collected from different sides of the mountain at different latitudes between July and August of 2009. The ∑PAH concentrations were within the range 38.5-190.1 ng g(-1) on the northern side, 117.7-443.6 ng g(-1) on the southern side, and 75.3-437.3 ng g(-1) on the western side. A progressive increase in the level of ∑PAHs with latitude was observed on the southern and western sides that face the westerly wind with abundant precipitation. However, a similar concentration gradient was not observed on the northern side that receives less rain and is on the leeward direction of the wind. The high-molecular-weight PAH compounds were predominant in the soils on the southern and western sides, while low-molecular-weight PAHs dominated the northern side soils. These findings show that the distribution of PAHs in the mountain soil is strongly influenced by the atmospheric long-range transport and cold trapping.
Colloidal gas aphron dispersions (CGAs) can be described as a system of microbubbles suspended homogenously in a liquid matrix. This work examines the performance of CGAs in comparison to surfactant solutions for washing low levels of arsenic from an iron rich soil. Sodium Dodecyl Sulfate (SDS) and saponin, a biodegradable surfactant, obtained from Sapindus mukorossi or soapnut fruit were used for generating CGAs and solutions for soil washing. Column washing experiments were performed in down-flow and up flow modes at a soil pH of 5 and 6 using varying concentration of SDS and soapnut solutions as well as CGAs. Soapnut CGAs removed more than 70% arsenic while SDS CGAs removed up to 55% arsenic from the soil columns in the soil pH range of 5-6. CGAs and solutions showed comparable performances in all the cases. CGAs were more economical since it contains 35% of air by volume, thereby requiring less surfactant. Micellar solubilization and low pH of soapnut facilitated arsenic desorption from soil column. FT-IR analysis of effluent suggested that soapnut solution did not interact chemically with arsenic thereby facilitating the recovery of soapnut solution by precipitating the arsenic. Damage to soil was minimal arsenic confirmed by metal dissolution from soil surface and SEM micrograph.
The aquatic ecotoxicity of chemicals involved in the manufacturing process of thin film transistor liquid crystal displays was assessed with a battery of four selected acute toxicity bioassays. We focused on tetramethylammonium hydroxide (TMAH, CAS No. 75-59-2), a widely utilized etchant. The toxicity of TMAH was low when tested in the 72 h-algal growth inhibition test (Pseudokirchneriellia subcapitata, EC50=360 mg L(-1)) and the Microtox® test (Vibrio fischeri, IC50=6.4 g L(-1)). In contrast, the 24h-microcrustacean immobilization and the 96 h-fish mortality tests showed relatively higher toxicity (Daphnia magna, EC50=32 mg L(-1) and Oryzias latipes, LC50=154 mg L(-1)). Isobologram and mixture toxicity index analyses revealed apparent synergism of the mixture of TMAH and potassium iodide when examined with the D. magna immobilization test. The synergistic action was unique to iodide over other halide salts i.e. fluoride, chloride and bromide. Quaternary ammonium ions with longer alkyl chains such as tetraethylammonium and tetrabutylammonium were more toxic than TMAH in the D. magna immobilization test.
In this work, the cytotoxicity and toxicity of phosphonium-based deep eutectic solvents (DESs) with three hydrogen bond donors, namely glycerine, ethylene glycol, and triethylene glycol were investigated. The cytotoxicity effect was tested using brine shrimp (Artemia salina). The toxicity was investigated using the two Gram positive bacteria Bacillus subtilis and Staphylococcus aureus, and two Gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. The cytotoxicity of tested DESs was much higher than that of their individual components, indicating their toxicological behavior was different. It was also found that there was toxic effect on the studied bacteria, indicating their potential application as anti-bacterial agents. To the best of our knowledge, this is the first time the cytotoxicity and toxicity of phosphonium-based DESs were studied.
The optical properties of a ZnO photocatalyst were enhanced with various dopant concentrations of Fe(3+). Doped ZnO nanoparticles were synthesized via a sol-gel method without the use of capping agents or surfactants and was then characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet-visible (UV-Vis) spectroscopy. The results showed that ZnO has a wurtzite, hexagonal structure and that the Fe(3+) ions were well incorporated into the ZnO crystal lattice. As the Fe(3+) concentration increased from 0.25 wt.% to 1 wt.%, the crystal size decreased in comparison with the undoped ZnO. The spectral absorption shifts of the visible light region (red shift) and the band gap decreases for each Fe-ZnO sample were investigated. The photocatalytic activities of the ZnO and Fe-ZnO samples were evaluated based on the degradation of 2-chlorophenol in aqueous solution under solar radiation. The samples with a small concentration of Fe(3+) ions showed enhanced photocatalytic activity with an optimal maximum performance at 0.5 wt.%. The results indicated that toxicity removal of 2-chlorophenol at same line of degradation efficiency. Small crystallite size and low band gap were attributed to high activities of Fe-ZnO samples under various concentrations of Fe(3+) ions compared to undoped ZnO.
This study was conducted to determine the composition and source apportionment of surfactant in atmospheric aerosols around urban and semi-urban areas in Malaysia based on ionic compositions. Colorimetric analysis was undertaken to determine the concentrations of anionic surfactants as Methylene Blue Active Substances (MBAS) and cationic surfactants as Disulphine Blue Active Substances (DBAS) using a UV spectrophotometer. Ionic compositions were determined using ion chromatography for cations (Na(+), NH4(+), K(+), Mg(2+), Ca(2+)) and anions (F(-), Cl(-), NO3(-), SO4(2-)). Principle component analysis (PCA) combined with multiple linear regression (MLR) were used to identify the source apportionment of MBAS and DBAS. Results indicated that the concentrations of surfactants at both sampling sites were dominated by MBAS rather than DBAS especially in fine mode aerosols during the southwest monsoon. Three main sources of surfactants were identified from PCA-MLR analysis for MBAS in fine mode samples particularly in Kuala Lumpur, dominated by motor vehicles, followed by soil/road dust and sea spray. Besides, for MBAS in coarse mode, biomass burning/sea spray were the dominant source followed by motor vehicles/road dust and building material.
Freshwater quality criteria for copper (Cu), cadmium (Cd), aluminum (Al), and manganese (Mn) were developed with particular reference to aquatic biota in Malaysia, and based on USEPA's guidelines. Acute toxicity tests were performed on eight different freshwater domestic species in Malaysia, which were Macrobrachiumlanchesteri (prawn), two fish -Poeciliareticulata and Rasborasumatrana, Melanoidestuberculata (snail), Stenocyprismajor (ostracod), Chironomusjavanus (midge larvae), Naiselinguis (annelid), and Duttaphrynusmelanostictus (tadpole), to determine 96-h LC50 values for Cu, Cd, Al, and Mn. The final acute values (FAVs) for Cu, Cd, Al, and Mn were 2.5, 3.0, 977.8, and 78.3 μgL(-1), respectively. Using an estimated acute-to-chronic ratio (ACR) of 8.3, the value for final chronic value (FCV) was derived. Based on FAV and FCV, a Criterion Maximum Concentration (CMC) and a criterion Continuous Concentration (CCC) for Cu, Cd, Al, and Mn of 1.3, 1.5, 488.9, and 39.1 μgL(-1) and 0.3, 0.36, 117.8, and 9.4 μgL(-1), respectively, were derived. The results of this study provide useful data for deriving national or local water quality criteria for Cu, Cd, Al, and Mn based on aquatic biota in Malaysia. Based on LC50 values, this study indicated that R.sumatrana, M.lanchesteri, C.javanus, and N.elinguis were the most sensitive to Cu, Cd, Al, and Mn, respectively.
In continuation of investigation for environmentally benign protocol for new solvents termed deep eutectic solvents (DESs), it is herein reported results concerning the toxicity and cytotoxicity of choline chloride (ChCl) based DESs with four hydrogen bond donors including glycerine, ethylene glycol, triethylene glycol and urea. The toxicity was investigated using two Gram positive bacteria Bacillus subtilis and Staphylococcus aureus, and two Gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. The cytotoxicity effect was tested using the Artemia salina leach. It was found that there was no toxic effect for the tested DESs on all of the studied bacteria confirming their benign effects on these bacteria. Nevertheless, it was found that the cytotoxicity of DESs was much higher than their individual components (e.g. glycerine, ChCl) indicating that their toxicological behavior is different. For our best knowledge this is the first time that toxicity and cytotoxicity of DESs were studied. The toxicity and cytotoxicity of DESs varied depending on the structure of components. Careful usage of the terms non-toxicity and biodegradability must be considered. More investigation on this matter is required.
In Asian developing countries, large amounts of municipal wastes are dumped into open dumping sites each day without adequate management. This practice may cause several adverse environmental consequences and increase health risks to local communities. These dumping sites are contaminated with many chemicals including brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). BFRs may be released into the environment through production processes and through the disposal of plastics and electronic wastes that contain them. The purpose of this study was to elucidate the status of BFR pollution in municipal waste dumping sites in Asian developing countries. Soil samples were collected from six open waste dumping sites and five reference sites in Cambodia, India, Indonesia, Malaysia, and Vietnam from 1999 to 2007. The results suggest that PBDEs are the dominant contaminants in the dumping sites in Asian developing countries, whereas HBCD contamination remains low. Concentrations of PBDEs and HBCDs ranged from ND to 180 μg/kg dry wt and ND to 1.4 μg/kg dry wt, respectively, in the reference sites and from 0.20 to 430 μg/kg dry wt and ND to 2.5 μg/kg dry wt, respectively, in the dumping sites. Contamination levels of PBDEs in Asian municipal dumping sites were comparable with those reported from electronic waste dismantling areas in Pearl River delta, China.
A series of experiments were carried out to determine the best medium for the recovery of cobalt by means of an electrogenerative system. Use of the electrogenerative system with a chloride medium had shown promising performance with the highest free energy of -389.8 kJ mol(-1) compared to that with sulphate and nitrate media. Subsequently, the influence of catholyte concentrations on cobalt recovery using the electrogenerative process was carried out by varying the initial cobalt concentration and sodium chloride concentration. The results showed that almost 100% recovery was attained within 1-4 h of the recovery process. Influence of pH was investigated where the electrogenerative system performed best between pH 5.0 and 7.0. Maximum cell performance of 83% with 99% cobalt removal was obtained at 90 min when 100 mg L(-1) of Co(2+) in 0.5 M NaCl was taken as catholyte solution. The values of ΔH(o) and ΔS(o) of the process were evaluated as 33.41 kJ mol(-1) and 0.13 kJ mol(-1), respectively.
Wetlands are an important source of DOM. However, the quantity and quality of wetlands' DOM from various climatic regions have not been studied comprehensively. The relationship between the concentrations of DOM (DOC), humic substances (HS) and non-humic substances (NHS) in wetland associated sloughs, streams and rivers, in cool temperate (Hokkaido, Japan), sub-tropical (Florida, USA), and tropical (Sarawak, Malaysia) regions was investigated. The DOC ranged from 1.0 to 15.6 mg CL(-1) in Hokkaido, 6.0-24.4 mg CL(-1) in Florida, and 18.9-75.3 mg CL(-1) in Sarawak, respectively. The relationship between DOC and HS concentrations for the whole sample set was regressed to a primary function with y-intercept of zero (P<0.005) and a slope value of 0.841. A similar correlation was observed between DOC and NHS concentrations, with a smaller slope value of 0.159. However, the correlation coefficient of the latter was much larger when the data was regressed to a logarithmic curve. These observations suggest the presence of a general tendency that the increased DOC in the river waters was mainly due to the increased supply of HS from wetland soils, whereas the rate of the increase in the NHS supply has an upper limit which may be controlled by primary productivity.
A study to assess the level of organochlorine pesticides (OCPs) and bisphenol A (BPA) in edible marine biota collected from coastal waters of Malaysia was conducted using GC-MS and SPE extraction. An analytical method was developed and validated to measure the level of 15 OCPs and BPA simultaneously from five selected marine species. It was observed that some samples had low levels of p,p'-DDE, p,p'-DDT and p,p'- DDD ranging from 0.50 ng g(-1) to 22.49 ng g(-1) dry weight (d.w) but significantly elevated level of endosulfan I was detected in a stingray sample at 2880 ng g(-1) d.w. BPA was detected in 31 out of 57 samples with concentration ranging from below quantification level (LOQ: 3 ng g(-1)) to 729 ng g(-1) d.w. The presence of OCPs is most likely from past use although there is also indication of illegal use in recent times. The study also reveals that BPA is more widely distributed in coastal species caught off the coast of the most developed state. The potential health risk from dietary intakes of OCPs and BPA from the analysed fish species was negligible.