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.
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.
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.
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.
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.
A study on the modification of rice husk by various carboxylic acids showed that tartaric acid modified rice husk (TARH) had the highest binding capacities for Cu and Pb. The carboxyl groups on the surface of the modified rice husk were primarily responsible for the sorption of metal ions. A series of batch experiments using TARH as the sorbent for the removal of Cu and Pb showed that the sorption process was pH dependent, rapid and exothermic. The sorption process conformed to the Langmuir isotherm with maximum sorption capacities of 29 and 108 mg/g at 27 +/- 2 degrees C for Cu and Pb, respectively. The uptake increased with agitation rate. Decrease in sorbent particle size led to an increase in the sorption of metal ions and this could be explained by an increase in surface area and hence binding sites. Metal uptake was reduced in the presence of competitive cations and chelators. The affinity of TARH for Pb is greater than Cu.
Iron(III)-poly(hydroxamic acid) resin complex has been studied for its sorption abilities with respect to arsenate and arsenite anions from an aqueous solution. The complex was found effective in removing the arsenate anion in the pH range of 2.0 to 5.5. The maximum sorption capacity was found to be 1.15 mmol/g. The sorption selectivity showed that arsenate sorption was not affected by chloride, nitrate and sulphate. The resin was tested and found effective for removal of arsenic ions from industrial wastewater samples.
The haze episodes that occurred in Malaysia in September-October 1991, August-October 1994 and September-October 1997 have been attributed to suspended smoke particulate matter from biomass burning in southern Sumatra and Kalimantan, Indonesia. In the present study, polar organic compounds in aerosol particulate matter from Malaysia are converted to their trimethylsilyl derivatives and analyzed by gas chromatography-mass spectrometry in order to better assess the contribution of the biomass burning component during the haze episodes. On the basis of this analysis, levoglucosan was found to be the most abundant organic compound detected in almost all samples. The monosaccharides, alpha- and beta-mannose, the lignin breakdown products, vanillic and syringic acids and the minor steroids, cholesterol and beta-sitosterol were also present in some samples. The presence of the tracers from smoke overwhelmed the typical signatures of emissions from traffic and other anthropogenic activities in the urban areas.
Co-pyrolysis of brominated flame retardants (BFRs) with polymeric materials prevails in scenarios pertinent to thermal recycling of bromine-laden objects; most notably the non-metallic fraction in e-waste. Hydro-dehalogenation of aromatic compounds in a hydrogen-donating medium constitutes a key step in refining pyrolysis oil of BFRs. Chemical reactions underpinning this process are poorly understood. Herein, we utilize accurate density functional theory (DFT) calculations to report thermo-kinetic parameters for the reaction of solid polyethylene, PE, (as a surrogate model for aliphatic polymers) with prime products sourced from thermal decomposition of BFRs, namely, HBr, bromophenols; benzene, and phenyl radical. Facile abstraction of an ethylenic H by Br atoms is expected to contribute to the formation of abundant HBr concentrations in practical systems. Likewise, a relatively low energy barrier for aromatic Br atom abstraction from a 2-bromophenol molecule by an alkyl radical site, concurs with the reported noticeable hydro-debromination capacity of PE. Pathways entailing a PE-induced bromination of a phenoxy radical should be hindered in view of high energy barrier for a Br transfer into the para position of the phenoxy radical. Adsorption of a phenoxy radical onto a Cu(Br) site substituted at the PE chain affords the commonly discussed PBDD/Fs precursor of a surface-bounded bromophenolate adduct. Such scenario arises due to the heterogeneous integration of metals into the bromine-rich carbon matrix in primitive recycling of e-waste and their open burning.
Contamination of endocrine disrupting compounds (EDCs) in tap water is an emerging global issue, and there are abundant influencing factors that have an ambivalent eﬀect on their transportation and fate. Different housing types vary in terms of water distribution system operation and design, water consumption choices, and other hydraulic factors, which potentially affect the dynamics, loadings, and partitioning of pollutants in tap water. Thus, this study analyzed 18 multiclass EDCs in tap water from different housing types (i.e., landed and high-rise) and the associated health risks. Sample analyses revealed the presence of 16 EDCs, namely hormones (5), pharmaceuticals (8), a pesticide (1), and plasticizers (2) in tap water, with the prevalent occurrence of bisphenol A up to 66.40 ng/L in high-rise housing. The presence of caffeine and sulfamethoxazole distribution in tap water was significantly different between landed and high-rise housings (t(152) = -2.298, p = 0.023 and t(109) = 2.135, p = 0.035). Moreover, the salinity and conductivity of tap water in high-rise housings were significantly higher compared to those in landed housings (t(122) = 2.411, p = 0.017 and t(94) = 2.997, p = 0.003, respectively). Furthermore, there were no potential health risks of EDCs (risk quotient
The emission of waste anaesthetic gas is a growing contributor to global warming and remains a factor in atmospheric ozone depletion. Volatile anaesthetics in medical waste gases could be removed via adsorption using suitable activated carbon materials possessing an enhanced affinity to anaesthetic molecules. In this work, the effects of surface physical and chemical properties on sevoflurane adsorption were investigated by oxidative hydrothermal surface modification of a commercial activated carbon using only distilled water. The hydrothermal surface modification was carried out at different treatment temperatures (150-300 °C) for varying durations (10-30 min), and adsorption was conducted under fixed conditions (bed depth = 10 cm, inlet concentration = 528 mg/L, and flow rate = 3 L/min). The hydrothermal treatment generally increased the BET surface area of the activated carbons. At oxidation temperatures above 200 °C, the micropore volume of the samples diminished. The relative amount of surface oxygen was enriched as the treatment temperature increased. Treatment duration did not significantly affect the introduction of relative amount of surface oxygen, except at higher temperatures. There were no new types of functional groups introduced. However, disappearance and re-formation of oxygen functional groups containing C-O structures (as in hydroxyl and ether groups) occurred when treatment temperature was increased from 150 to 200 °C, and when treatments were conducted above 200 °C, respectively. The ester/acetal groups were enriched under the temperature range studied. The findings suggested that the re-formation of surface oxygen functionalities might lead to the development of functional groups that improve sevoflurane adsorption.
Recently, the production of renewable biogas such as biohydrogen and biomethane from wastewaters through anaerobic fermentation has gained worldwide attention. In the present study, a mobile bioenergy generation station had been constructed based on a high-efficiency hydrogenesis & methanogenesis technology (HyMeTek) developed by Feng Chia University, Taiwan. The substrate was a beverage wastewater having chemical oxygen demand (COD) concentration of 1200 mg/L. This bioenergy station had a feedstock tank (3.8 m3), a nutrient tank (0.8 m3), an acidogenesis tank (AT, 2 m3), two methanogenesis tanks (MT, 4 m3 for each), a membrane bioreactor and a control room. Biogas production rate, methane concentration, COD removal efficiencies, energy efficiency and economical interest of the plant were assessed. The peak total methane production rates for AT (at hydraulic retention time, HRT, 4 h) and MT (at HRT 8 h) were 430 and 7 mL/L·d, respectively. A strategy of shortening HRT was a promising method to enhance biogas quality and energy efficiency. This mobile bioenergy system has commercial potential because it could bring good economic benefit of initial rate of return (58.84%) and payback time (2.68 y).
Since a few centuries ago, organochlorine compounds (OCs) become one of the threatened contaminants in the world. Due to the lipophilic and hydrophobic properties, OCs always discover in fat or lipid layers through bioaccumulation and biomagnification. The OCs are able to retain in soil, sediment and water for long time as it is volatile, OCs will evaporate from soil and condense in water easily and frequently, which pollute the shelter of aquatic life and it affects the function of organs and damage system in human body. Photocatalysis that employs the usage of semiconductor nanophotocatalyst and solar energy can be the possible alternative for current conventional water remediation technologies. With the benefits of utilizing renewable energy, no production of harmful by-products and easy operation, degradation of organic pollutants in rural water bodies can be established. Besides, nanophotocatalyst that is synthesized with nanotechnology outnumbered conventional catalyst with larger surface area to volume ratio, thus higher photocatalytic activity is observed. In contrast, disadvantages particularly no residual effect in water distribution network, requirement of post-treatment and easily affected by various factors accompanied with photocatalysis method cannot be ignored. These various factors constrained the photocatalytic efficiency via nanocatalysts which causes the full capacity of solar photocatalysis has yet to be put into practice. Therefore, further modifications and research are still required in nanophotocatalysts' synthesis to overcome limitations such as large band gaps and photodecontamination.
Vulcanized rubber, due to its superior mechanical properties, has long been used in various industries, especially automotive. The rubber industry has evolved and expanded over the years to meet the increasing global demands for tires. Today tires consist of about 19% natural rubber and 24% synthetic rubber, while plastic polymer and metal, filler and additives make up the rest. Over 1.6 billion new tires are produced annually and around 1 billion waste tires are generated. Tires are extensively designed with several complex processes to make them virtually indestructible. Since tire rubber does not decompose easily, their disposal at the end of service life creates a monumental environmental impact. However, waste tire rubber (WTR) consist of valuable rubber hydrocarbon, making its recovery or regeneration highly desirable. The conventional recovery method of WTR tends to produce undesirable products due to the destruction of the polymeric chain and exponentially degenerates the vulcanizates' physical properties. Since then, multiple devulcanization processes were introduced to effectively and selectively cleave vulcanizate's crosslinks while retaining the polymeric networks. Different devulcanization methods such as chemical, mechanical, irradiation, biological and their combinations that have been explored until now are reviewed here. Besides, an overview of the latest development of devulcanization by ionic liquids and deep eutectic solvents are also described. While such devulcanization technique provides new sustainability pathway(s) for WTR, the generated devulcanizate also possesses comparable physical properties to that of virgin products. This further opens the possibility of novel circular economic opportunities worldwide.
In this study, to improve the mechanical and thermal properties of curdlan film, a curdlan/nanocellulose (NC) blended film was prepared and characterized for the first time. NC was successfully prepared from microcrystalline cellulose (MCC) with NaOH/urea treatment. The particle size of NC was observed to be 70-140 nm by cryo-electron microscope (cryo-EM). The blended film was prepared by adding the NC to curdlan solution. The tensile strength (TS) of the blended film reached the maximum value of 38.6 MPa, and the elongation at break (EB) was 40%. The DSC curve showed that the heat absorption peak of the film was 240 °C, indicating that the blended film has good temperature stability. Additionally, some other film properties were also improved, including gas barrier properties and transparency. Obvious morphological and molecular differences between the blended film and the pure curdlan film were discovered by SEM and FTIR analysis. Finally, the blended film was used for the preservation of chilled meat and extended the storage time of meat to 12 days. These results provided a theoretical basis for future application and development of biodegradable film.
In this study, the performance of glyphosate removal in an electrocoagulation batch with two electrodes formed by the same metal type, consisting of aluminum, iron, steel and copper have been compared. The aim of this study intends to remove glyphosate from an aqueous solution by an electrocoagulation process using metal electrode plates, which involves electrogeneration of metal cations as coagulant agents. The production of metal cations showed an ability to bind together to form aggregates of flocs composed of a combination of glyphosate and metal oxide. Electrocoagulation using aluminum electrodes indicated a high percentage removal of glyphosate, 94.25%; followed by iron electrodes, 88.37%; steel electrodes, 62.82%; and copper electrodes, 46.69%. The treated aqueous solution was then analyzed by Fourier Transform Infrared Spectroscopy. Percentages of Carbon, Hydrogen, Nitrogen, Sulfur remaining in the treated aqueous solution after the electrocoagulation process have been determined. The treated water and sludge were characterized and the mechanism of the overall process was concluded as an outcome. An X-Ray Diffraction analysis of dried sludge confirmed that new polymeric compounds were formed during the treatment. The sludge composed of new compounds were also verified the removals. This study revealed that an electrocoagulation process using metal electrodes is reliable and efficient.
In this study, palm shell activated carbon powder (PSAC) and magnesium silicate (MgSiO3) modified PSAC (MPSAC) were thoroughly investigated for fluoride (F-) adsorption. F- adsorption isotherms showed that PSAC and MPSAC over-performed some other reported F- adsorbents with adsorption capacities of 116 mg g-1 and 150 mg g-1, respectively. Interestingly, the MgSiO3 impregnated layer changed the adsorption behavior of F- from monolayer to heterogeneous multilayer based on the Langmuir and Freundlich isotherm models verified by chi-square test (X2). Thermodynamic parameters indicated that the F- adsorption on PSAC and MPSAC was spontaneous and exothermic. PSAC and MPSAC were characterized using FESEM-EDX, XRD, FTIR and XPS to investigate the F- adsorption mechanism. Based on the regeneration tests using NaOH (0.01 M), PSAC exhibited poor regeneration (<20%) while MPSAC had steady adsorption efficiencies (∼70%) even after 5 regeneration cycles. This is due to highly polarized C-F bond was found on PSAC while Mg-F bond was distinguished on MPSAC, evidently denoting that the F- adsorption is mainly resulted from the exchange of hydroxyl (-OH) group. It was concluded that PSAC would be a potential adsorbent for in-situ F- groundwater remediation due to its capability to retain F- without leaching out in a wide range pH. MPSAC would be an alternative adsorbent for ex-situ F- water remediation because it can easily regenerate with NaOH solution. With the excellent F- adsorption properties, both PSAC and MPSAC offer as promising adsorbents for F- remediation in the aqueous phase.
Efforts to improve water quality have led to the development of green and sustainable water treatment approaches. Herein, nitrogen-doped magnetized hydrochar (mSBHC-N) was synthesized, characterized, and used for the removal of post-transition and transition heavy metals, viz. Pb2+ and Cd2+ from aqueous environment. mSBHC-N was found to be mesoporous (BET surface area - 62.5 m2/g) and paramagnetic (saturation magnetization - 44 emu/g). Both, FT-IR (with peaks at 577, 1065, 1609 and 3440 cm-1 corresponding to Fe - O stretching vibrations, C - N stretching, N - H in-plane deformation and stretching) and XPS analyses (with peaks at 284.4, 400, 530, 710 eV due to C 1s, N 1s, O 1s, and Fe 2p) confirmed the presence of oxygen and nitrogen containing functional groups on mSBHC-N. The adsorption of Pb2+ and Cd2+ was governed by oxygen and nitrogen functionalities through electrostatic and co-ordination forces. 75-80% of Pb2+ and Cd2+ adsorption at Co: 25 mg/L, either from deionized water or humic acid solution was accomplished within 15 min. The data was fitted to pseudo-second-order kinetic and Langmuir isotherm models, with maximum monolayer adsorption capacities being 323 and 357 mg/g for Cd2+and Pb2+ at 318 K, respectively. Maximum Cd2+ (82.6%) and Pb2+ (78.7%) were eluted with 0.01 M HCl, simultaneously allowing minimum iron leaching (2.73%) from mSBHC-N. In conclusion, the study may provide a novel, economical, and clean route to utilize agro-waste, such as sugarcane bagasse (SB), for aquatic environment remediation.
The geochemistry and distribution of major, trace and rare earth elements (REE's) was studied in the surface sediments of the Lower Baram River during two seasons: the Monsoon (MON) and Post - monsoon (POM). The major geochemical processes controlling the distribution and mobility of major, trace and REE's in the Lower Baram River surface sediments was revealed through factor analysis. The risk assessment of major and trace element levels was studied at three specific levels; i.e. the enrichment level [Contamination Factor (Cf), with the geo-accumulation index (Igeo)], the availability level [metals bound to different fractions, risk assessment code (RAC)], and the biological toxicity level [effect range low (ERL) and effect range medium (ERM)]. The results of all the indices indicate that Cu is the element of concern in the Lower Baram River sediments. The geochemical fractionation of major and trace elements were studied through sequential extraction and the results indicated a higher concentration of Mn in the exchangeable fraction. The element of concern, Cu, was found to be highly associated in the organic bound (F4) fraction during both seasons and a change in the redox, possibly due to storms or dredging activities may stimulate the release of Cu into the overlying waters of the Lower Baram River.
This study aimed to determine the distribution and potential health risks of polycyclic aromatic hydrocarbons (PAHs) in PM2.5 collected in Kuala Lumpur during different monsoon seasons. The potential sources of PM2.5 were investigated using 16 priority PAHs with additional of biomass tracers namely levoglucosan (LV), mannosan (MN) and galactosan (GL). This study also investigated the cytotoxic potential of the extracted PAHs towards V79-4 cells. A high-volume air sampler (HVS) was used to collect PM2.5 samples for 24 h. PAHs were extracted using dichloromethane (DCM) while biomass tracers were extracted by a mixture of DCM/methanol (3:1) before analysis with gas chromatography-mass spectrometry (GC-MS). The cytotoxicity of the PAHs extract was determined by assessing the cell viability through the reduction of tetrazolium salts (MTT). The results showed that the total mean ± SD concentrations of PAHs during the southwest (SW) and northeast (NE) monsoons were 2.51 ± 0.93 ng m-3 and 1.37 ± 0.09 ng m-3, respectively. Positive matrix factorization (PMF) using PAH and biomass tracer concentrations suggested four potential sources of PM2.5; gasoline emissions (29.1%), natural gas and coal burning (28.3%), biomass burning (22.3%), and diesel and heavy oil combustion (20.3%). Health risk assessment showed insignificant incremental lifetime cancer risk (ILCR) of 2.40E-07 for 70 years of exposure. MTT assay suggested that PAHs extracts collected during SW monsoon have cytotoxic effect towards V79-4 cell at the concentrations of 25 μg mL-1, 50 μg mL-1, 100 μg mL-1 whereas non-cytotoxic effect was observed on the PAHs sample collected during NE monsoon.