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.
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.
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.
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.
The present study examined the concentrations of mercury (Hg), methylmercury (MeHg), and selenium (Se) in the multiple tissues of the Plotosus canius and Periophthalmodon schlosseri collected from the Strait of Malacca. The mean value in mg kg(-1) of Hg (P. canius: 0.34 ± 0.19; P. schlosseri: 0.32 ± 0.18) and MeHg in muscle (P. canius: 0.14 ± 0.11; P. schlosseri: 0.17 ± 0.11) were below the Codex general standard for contaminants and toxins in food and feed (CODEX STAN 193-1995), the Malaysian Food Regulation 1985 and the Japan Food Sanitation Law. For P. canius, the liver contained the highest concentrations of Hg (0.48 ± 0.07 mg kg(-1)) and MeHg (0.21 ± 0.00 mg kg(-1)), whereas for P. schlosseri, the gill contained the highest concentrations of Hg (0.36 ± 0.06 mg kg(-1)) and MeHg (0.21 ± 0.05 mg kg(-1)). The highest concentration of (80)Se (mg kg(-1)) was observed in the liver of P. canius (20.34 ± 5.68) and in the gastrointestinal tract (3.18 ± 0.42) of P. schlosseri. The selenium:mercury (Se:Hg) molar ratios were above 1 and the positive selenium health benefit value (HBVSe) suggesting the possible protective effects of Se against Hg toxicity. The estimate weekly intakes (EWIs) in μg kg(-1) body weight (bw) week(-1) of Hg (P. canius: 0.27; P. schlosseri: 0.15) and MeHg (P. canius: 0.11; P. schlosseri: 0.08) were found to be lower than the provisional tolerable weekly intake established by the Joint FAO/WHO Expert Committee on Food Additives (JECFA). Based on the calculated EWIs, P. canius, and P. schlosseri were found to be unlikely to cause mercury toxicity in human consumption.
Triethoxyphenylsilane (TEPS)-functionalized magnetic palm-based powdered activated carbon (MPPAC-TEPS) was prepared and characterized using various spectroscopic methods, and then tested for the removal of bisphenol A, carbamazepine, ibuprofen and clofibric acid. Magnetite film on MPPAC-TEPS was homogeneously coated on the outer surface of palm-based powdered activated carbon (PPAC) through a hydrothermal co-precipitation technique. Followed by silanization of phenyl-functionalized organosilane on MPPAC's magnetic film. As results, micro/mesopore surface area and volume increased without significant pore clogging and iron (Fe) dissolution under the acidic conditions was greatly decreased. The unique structural and chemical features of MPPAC-TEPS were found to be the main reasons for the enhanced adsorption rates and removal capacities of POPs. The presence of electrolytes and different pH values greatly affected the sorption efficiencies. The dominant sorption mechanism of POPs by MPPAC-TEPS was determined to be π-π interaction (physisorption), based on thermodynamic (ΔG°) and differential scanning calorimetry (DSC). Thermal regeneration at a low temperature (350 °C) was an effective method to desorb the retained POPs and enabled to reactivate MPPAC-TEPS with sustained sorption rates and capacities, whereas PPAC was largely exhausted. As a new type of sorbent for POPs, MPPAC-TEPS has operational advantages, such as magnetic separation and stable regeneration.
Malaysia, a rapidly growing industrial country, is susceptible to pollution via large-scale industrial engagements and associated human activities. One particular concern is the potential impact upon the quality of locally resourced vegetables, foodstuffs that contain important nutrients necessary for good health, forming an essential part of the Malaysian diet. As a part of this, it is of importance for there to be accurate knowledge of radioactive material uptake in these vegetables, not least in respect of any public health detriment. Herein, using HPGe γ-ray spectrometry, quantification has been performed of naturally occurring radionuclides in common edible vegetables and their associated soils. From samples analyses, the soil activity concentration ranges (in units of Bq/kg) for (226)Ra, (232)Th and (40)K were respectively 1.33-30.90, 0.48-26.80, 7.99-136.5 while in vegetable samples the ranges were 0.64-3.80, 0.21-6.91, 85.53-463.8. Using the corresponding activities, the transfer factors (TFs) from soil-to-vegetables were estimated, the transfers being greatest for (40)K, an expected outcome given the essentiality of this element in support of vigorous growth. The TFs of (226)Ra and (232)Th were found to be in accord with available literature data, the values indicating the mobility of these radionuclides to be low in the studied soils. Committed effective dose and the associated life-time cancer risk was estimated, being found to be below the permissible limit proposed by UNSCEAR. Results for the studied media show that the prevalent activities and mobilities pose no significant threat to human health, the edible vegetables being safe for consumption.
In this study, chars from coconut pith (CP) were prepared aiming for superior adsorption towards elemental mercury (Hg(o)). The yield, proximate analysis, textural characteristics, surface functional groups and elemental composition analyses of the chars produced at pyrolysis temperature of 300 °C, 500 °C, 700 °C and 900 °C were compared. The surface area, pore volume, ash and carbon content of chars increased, while the yield and moisture content decreased with increasing pyrolysis temperatures. The changing of physical and chemical properties of the chars produced at variety pyrolysis temperature was much effect on the Hg(o) adsorption performance and definitely provides important information on the Hg(o) adsorption mechanism. The highest Hg(o) adsorption capacity was observed for CP900 (6067.49 μg/g), followed by CP700 (2395.98 μg/g), CP500 (289.76 μg/g), CP300 (1.68 μg/g), and CP (0.73 μg/g). The equilibrium data were well described by the Freundlich adsorption isotherm model. The pseudo-second order best described the kinetic data of the Hg(o) adsorption onto CP and CP300. For chars produced at higher pyrolysis temperature, however, the pseudo-zero order and pseudo-second order fitted well for the adsorption and breakthrough regions, respectively. The Hg(o) adsorption capacity of chars obtained from high pyrolysis temperature of CP significantly outperformed the commercial activated carbon (Darco KB-B) as well as superior to chars reported in the literature indicating the CP can be used as a precursor for preparation of chars as elemental mercury adsorbents.
This study evaluates the impact of anthropogenic activities on the Shahrood River using water physico-chemical variables and macroinvertebrates data sets obtained over a period of 12 months between February 2012 and February 2013 at 8 sampling sites. Biotic indices i.e. FBI and BMWP based on macroinvertebrates and physico-chemical indices (MPI, HPI and NSF-WQI) were employed to evaluate the water quality status in connection with natural- and human-induced pressures. Based on physico-chemical indices, water quality was categorized as low polluted level and it is suitable for drinking purposes. The water quality based on biotic indices was related to the anthropic activities; a clear deterioration of the water quality was observed from upstream to downstream sites. The water quality along the river changed from very good (class I; reference sites) to good (class II; midstream sites) and turned into moderate (class III) and poor (class IV) quality (downstream sites). These findings indicate that biotic indices are more powerful indicators in assessing water quality than physico-chemical indices. Allocapnia, Glossosoma and Hesperoperla were exclusively related to least disturbed sites, and Naididae, Orthocladiinae and Ecdyonurus were found in sites showing notable degradation. Our results recommended that the use of macroinvertebrates could be employed as a cost-effective tool for biomonitoring and controlling of polluted riverine ecosystems in the Middle East. Finally, the results from this study may be useful not only for developing countries, but also for any organization struggling to use macroinvertebrate based indices with restricted financial resources and knowledge.
In recent years, environmental concerns over ultra-trace levels of steroid estrogens concentrations in water samples have increased because of their adverse effects on human and animal life. Special attention to the analytical techniques used to quantify steroid estrogens in water samples is therefore increasingly important. The objective of this review was to present an overview of both instrumental and non-instrumental analytical techniques available for the determination of steroid estrogens in water samples, evidencing their respective potential advantages and limitations using the Need, Approach, Benefit, and Competition (NABC) approach. The analytical techniques highlighted in this review were instrumental and non-instrumental analytical techniques namely gas chromatography mass spectrometry (GC-MS), liquid chromatography mass spectrometry (LC-MS), enzyme-linked immuno sorbent assay (ELISA), radio immuno assay (RIA), yeast estrogen screen (YES) assay, and human breast cancer cell line proliferation (E-screen) assay. The complexity of water samples and their low estrogenic concentrations necessitates the use of highly sensitive instrumental analytical techniques (GC-MS and LC-MS) and non-instrumental analytical techniques (ELISA, RIA, YES assay and E-screen assay) to quantify steroid estrogens. Both instrumental and non-instrumental analytical techniques have their own advantages and limitations. However, the non-instrumental ELISA analytical techniques, thanks to its lower detection limit and simplicity, its rapidity and cost-effectiveness, currently appears to be the most reliable for determining steroid estrogens in water samples.
Fourteen beta-agonists were quantitatively analyzed in cattle, chicken and swine liver specimens purchased at 14 wet markets in Selangor State, Malaysia, by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The health risks of ractopamine and clenbuterol residues in the Malaysian population were assessed based on quantitative data and meat consumption statistics in Malaysia. Wastewater samples collected at swine farms (n = 2) and cattle/cow farms (n = 2) in the Kuala Langat district were analyzed for the presence for the 14 compounds. Wastewater in chicken farms was not collected because there was negligible discharge during the breeding period. The environmental impacts caused by beta-agonists discharged from livestock farms were spatially assessed in the Langat River basin using a geographic information system (GIS). As a result, 10 compounds were detected in the liver specimens. Ractopamine, which is a permitted compound for swine in Malaysia, was frequently detected in swine livers; also, 9 other compounds that are prohibited compounds could be illegally abused among livestock farms. The health risks of ractopamine and clenbuterol were assessed to be minimal as their hazard quotients were no more than 7.82 × 10(-4) and 2.71 × 10(-3), respectively. Five beta-agonists were detected in the wastewater samples, and ractopamine in the swine farm resulted in the highest contamination (30.1 μg/L). The environmental impacts of the beta-agonists in the Langat River basin were generally concluded to be minimal, but the ractopamine contamination released from swine farms was localized in coastal areas near the estuary of the Langat River basin because most swine farms were located in that region.
Toxic elements in drinking water have great effects on human health. However, there is very limited information about toxic elements in drinking water in Afghanistan. In this study, levels of 10 elements (chromium, nickel, copper, arsenic, cadmium, antimony, barium, mercury, lead and uranium) in 227 well drinking water samples in Kabul, Afghanistan were examined for the first time. Chromium (in 0.9% of the 227 samples), arsenic (7.0%) and uranium (19.4%) exceeded the values in WHO health-based guidelines for drinking-water quality. Maximum chromium, arsenic and uranium levels in the water samples were 1.3-, 10.4- and 17.2-fold higher than the values in the guidelines, respectively. We next focused on uranium, which is the most seriously polluted element among the 10 elements. Mean ± SD (138.0 ± 1.4) of the (238)U/(235)U isotopic ratio in the water samples was in the range of previously reported ratios for natural source uranium. We then examined the effect of our originally developed magnesium (Mg)-iron (Fe)-based hydrotalcite-like compounds (MF-HT) on adsorption for uranium. All of the uranium-polluted well water samples from Kabul (mean ± SD = 190.4 ± 113.9 μg/L; n = 11) could be remediated up to 1.2 ± 1.7 μg/L by 1% weight of our MF-HT within 60 s at very low cost (<0.001 cents/day/family) in theory. Thus, we demonstrated not only elevated levels of some toxic elements including natural source uranium but also an effective depurative for uranium in well drinking water from Kabul. Since our depurative is effective for remediation of arsenic as shown in our previous studies, its practical use in Kabul may be encouraged.
Recently, deep eutectic solvents (DESs) have shown their new and interesting ability for chemistry through their involvement in variety of applications. This study introduces carbon nanotubes (CNTs) functionalized with DES as a novel adsorbent for Hg(2+) from water. Allyl triphenyl phosphonium bromide (ATPB) was combined with glycerol as the hydrogen bond donor (HBD) to form DES, which can act as a novel CNTs functionalization agent. The novel adsorbent was characterized using Raman, FTIR, XRD, FESEM, EDX, BET surface area, TGA, TEM and Zeta potential. Response surface methodology was used to optimize the removal conditions for Hg(2+). The optimum removal conditions were found to be pH 5.5, contact time 28 min, and an adsorbent dosage of 5 mg. Freundlich isotherm model described the adsorption isotherm of the novel adsorbent, and the maximum adsorption capacity obtained from the experimental data was 186.97 mg g(-1). Pseudo-second order kinetics describes the adsorption rate order.
Total mercury (THg) and methylmercury (MeHg) concentrations were determined from sediment samples collected from thirty sampling stations in Port Klang, Malaysia. Three stations had THg concentrations exceeding the threshold effect level of the Florida Department of Environmental Protection and the Canadian interim sediment quality guidelines. THg and MeHg concentrations were found to be concentrated in the Lumut Strait where inputs from the two most urbanized rivers in the state converged (i.e. Klang River and Langat River). This suggests that Hg in the study area likely originated from the catchments of these rivers. MeHg made up 0.06-94.96% of the sediment's THg. There is significant positive correlation (p
A new graphene-based tetraethoxysilane-methyltrimethoxysilane sol-gel hybrid magnetic nanocomposite (Fe3O4@G-TEOS-MTMOS) was synthesised, characterized and successfully applied in magnetic solid-phase extraction (MSPE) for simultaneous analysis of polar and non-polar organophosphorus pesticides from several water samples. The Fe3O4@G-TEOS-MTMOS nanocomposite was characterized using Fourier transform-infrared spectroscopy, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray diffraction. Separation, determination and quantification were achieved using gas chromatography coupled with micro electron capture detector. Adsorption capacity of the sorbent was calculated using Langmuir equation. MSPE was linear in the range 100-1000 pg mL(-1) for phosphamidon and dimethoate, and 10-100 pg mL(-1) for chlorpyrifos and diazinon, with limit of detection (S/N = 3) of 19.8, 23.7, 1.4 and 2.9 pg mL(-1) for phosphamidon, dimethoate, diazinon and chlorpyrifos, respectively. The LODs obtained is well below the maximum residual level (100 pg mL(-1)) as set by European Union for pesticides in drinking water. Acceptable precision (%RSD) was achieved for intra-day (1.3-8.7%, n = 3) and inter-day (7.6-17.8%, n = 15) analyses. Fe3O4@G-TEOS-MTMOS showed high adsorption capacity (54.4-76.3 mg g(-1)) for the selected OPPs. No pesticide residues were detected in the water samples analysed. Excellent extraction recoveries (83-105%) were obtained for the spiked OPPs from tap, river, lake and sea water samples. The newly synthesised Fe3O4@G-TEOS-MTMOS showed high potential as adsorbent for OPPs analysis.
Photocatalytic fuel cell (PFC) is a potential wastewater treatment technology that can generate electricity from the conversion of chemical energy of organic pollutants. An immobilized ZnO/Zn fabricated by sonication and heat attachment method was applied as the photoanode and Pt/C plate was used as the cathode of the PFC in this study. Factors that affect the decolorization efficiency and electricity generation of the PFC such as different initial dye concentrations and pH were investigated. Results revealed that the degradation of Reactive Green 19 (RG19) was enhanced in a closed circuit PFC compared with that of a opened circuit PFC. Almost 100% decolorization could be achieved in 8 h when 250 mL of 30 mg L(-1) of RG19 was treated in a PFC without any supporting electrolyte. The highest short circuit current of 0.0427 mA cm(-2) and maximum power density of 0.0102 mW cm(-2) was obtained by PFC using 30 mg L(-1) of RG19. The correlation between dye degradation, conductivity and voltage output were also investigated and discussed.
This study aims to develop a highly efficient adsorbent material. CNTs are prepared using a chemical vapor deposition method with acetylene and synthesized mesoporous Ni-MCM41 as the carbon source and catalyst, respectively, and are then functionalized using 3-aminopropyltriethoxysilane (APTES) through the co-condensation method and loaded with commercial TiO2. Results of X-ray powder diffraction (XRD), Raman spectra, and Fourier transform infrared spectroscopy (FTIR) confirm that the synthesized CNTs grown are multi-walled carbon nanotubes (MWNTs). Transmission electron microscopy shows good dispersion of TiO2 nanoparticles onto functionalized-CNTs loaded TiO2, with the diameter of a hair-like structure measuring between 3 and 8 nm. The functionalized-CNTs loaded TiO2 are tested as an adsorbent for removal of methyl orange (MO) in aqueous solution, and results show that 94% of MO is removed after 10 min of reaction, and 100% after 30 min. The adsorption kinetic model of functionalized-CNTs loaded TiO2 follows a pseudo-second order with a maximum adsorption capacity of 42.85 mg/g. This study shows that functionalized-CNTs loaded TiO2 has considerable potential as an adsorbent material due to the short adsorption time required to achieve equilibrium.
Ionic liquids (ILs) are class of solvent whose properties can be modified and tuned to meet industrial requirements. However, a high number of potentially available cations and anions leads to an even increasing members of newly-synthesized ionic liquids, adding to the complexity of understanding on their impact on aquatic organisms. Quantitative structure activity∖property relationship (QSAR∖QSPR) technique has been proven to be a useful method for toxicity prediction. In this work,σ-profile descriptors were used to build linear and non-linear QSAR models to predict the ecotoxicities of a wide variety of ILs towards bioluminescent bacterium Vibrio fischeri. Linear model was constructed using five descriptors resulting in high accuracy prediction of 0.906. The model performance and stability were ascertained using k-fold cross validation method. The selected descriptors set from the linear model was then used in multilayer perceptron (MLP) technique to develop the non-linear model, the accuracy of the model was further enhanced achieving high correlation coefficient with the lowest value being 0.961 with the highest mean square error of 0.157.
An air exposed single-chamber microbial fuel cell (SCMFC) using microalgal biocathodes was designed. The reactors were tested for the simultaneous biodegradation of real dye textile wastewater (RTW) and the generation of bioelectricity. The results of digital image processing revealed a maximum coverage area on the biocathodes by microalgal cells of 42%. The atmospheric and diffused CO2 could enable good algal growth and its immobilized operation on the cathode electrode. The biocathode-SCMFCs outperformed an open circuit voltage (OCV), which was 18%-43% higher than the control. Furthermore, the maximum volumetric power density achieved was 123.2 ± 27.5 mW m(-3). The system was suitable for the treatment of RTW and the removal/decrease of COD, colour and heavy metals. High removal efficiencies were observed in the SCMFCs for Zn (98%) and COD (92-98%), but the removal efficiencies were considerably lower for Cr (54-80%). We observed that this single chamber MFC simplifies a double chamber system. The bioelectrochemical performance was relatively low, but the treatment capacity of the system seems encouraging in contrast to previous studies. A proof-of-concept experiment demonstrated that the microalgal biocathode could operate in air exposed conditions, seems to be a promising alternative to a Pt cathode and is an efficient and cost-effective approach to improve the performance of single chamber MFCs.
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.