This study was conducted to investigate the potential application of oil palm empty fruit branches (OPEFB) as adsorbents to remove organic methylmercurry, MeHg(II), and inorganic Hg(II) from aqueous solution. The OPEFB was functionalized with amine containing ligand namely 3-ureidopropyltriethoxysilane (UPTES) aiming for better adsorption performance towards both mercury ions. The adsorption was found to be dependent on initial pH, initial concentraton, temperatures, and contact time. The maximum adsorption capacities (Qm.exp) of Hg(II) adsorption onto OPEFB and UPTES-OPEFB were 0.226 and 0.773 mmol/g, respectively. The Qm.exp of MeHg(II) onto OPEFB, however, was higher than UPTES-OPEFB. The adsorption kinetic data obeyed the Elovich model and the adsorption was controlled by the film-diffusion step. The calculated thermodynamic parameters indicate an endothermic adsorption process. Adsorption data analysis indicates that the adsorption mechanism may include ion-exchange, complexation, and physisorption interactions. The potential applications of adsorbents were demonstrated using oilfield produced water and natural gas condensate. The UPTES-OPEFB offered higher selectivity towards both mercury ions than OPEFB. The regenerability studies indicated that the adsorbent could be reused for multiple cycles.
The objective of this study was to examine the effect of washing pre-treatment on mercury concentration in fish fillet. Response surface methodology was used to investigate the influence of three variables, pH (1-6.5), NaCl (0-1% w/v) and exposure time (5-30 min) by using a three-factor central composite design. The aim was to obtain the best possible combination of these variables in order to reduce mercury in fish fillet. The experimental data were adequately fitted into a second-order polynomial model with multiple regression coefficients (R(2)) of 0.961. The results indicated that the reduction of mercury in fish flesh significantly depends on the pH of the solution used. The overall optimal condition resulting in the maximum mercury reduction in fish fillet was obtained at a combined level pH of 2.79, NaCl of 0.5% and exposure time of 13.5 min. The optimized protocol produced a solution that can reduce mercury from raw fish fillet up to 81%.
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.
Mercuric species, Hg(II), interacts strongly with dissolved organic matter (DOM) through the oxidation, reduction, and complexation that affect the fate, bioavailability, and cycling of mercury, Hg, in aquatic environments. Despite its importance, the reactions between Hg(II) and DOM have rarely been studied in the presence of different concentrations of chloride ions (Cl-) under anoxic conditions. Here, we report that the extent of Hg(II) reduction in the presence of the reduced DOM decreases with increasing Cl- concentrations. The rate constants of Hg(II) reduction ranged from 0.14 to 1.73 h-1 in the presence of Cl- and were lower than the rate constant (2.41 h-1) in the absence of Cl-. Using a thermodynamic model, we showed that stable Hg(II)-chloride complexes were formed in the presence of Cl-. We further examined that H(0) was oxidized to Hg(II) in the presence of the reduced DOM and Cl- under anoxic conditions, indicating that Hg(II) reduction is inhibited by the Hg(0) oxidation. Therefore, the Hg(II) reduction by the reduced DOM can be offset due to the Hg(II)-chloride complexation and Hg(0) oxidation in chloride-rich environments. These processes can significantly influence the speciation of Hg and have an important implication for the behavior of Hg under environmentally relevant concentrations.
Multi-walled carbon nanotubes (CNTs) functionalized with a deep eutectic solvent (DES) were utilized to remove mercury ions from water. An artificial neural network (ANN) technique was used for modelling the functionalized CNTs adsorption capacity. The amount of adsorbent dosage, contact time, mercury ions concentration and pH were varied, and the effect of parameters on the functionalized CNT adsorption capacity is observed. The (NARX) network, (FFNN) network and layer recurrent (LR) neural network were used. The model performance was compared using different indicators, including the root mean square error (RMSE), relative root mean square error (RRMSE), mean absolute percentage error (MAPE), mean square error (MSE), correlation coefficient (R2) and relative error (RE). Three kinetic models were applied to the experimental and predicted data; the pseudo second-order model was the best at describing the data. The maximum RE, R2 and MSE were 9.79%, 0.9701 and 1.15 × 10-3, respectively, for the NARX model; 15.02%, 0.9304 and 2.2 × 10-3 for the LR model; and 16.4%, 0.9313 and 2.27 × 10-3 for the FFNN model. The NARX model accurately predicted the adsorption capacity with better performance than the FFNN and LR models.
The preparation of chars and activated carbon as low-cost elemental mercury adsorbents was carried out through the carbonisation of coconut husk (pith and fibre) and the activation of chars with potassium hydroxide (KOH), respectively. The synthesised adsorbents were characterised by using scanning electron microscopy, Fourier transform infrared spectroscopy and nitrogen adsorption/desorption analysis. The elemental mercury removal performance was measured using a conventional flow type packed-bed adsorber. The physical and chemical properties of the adsorbents changed as a result of the carbonisation and activation process, hence affecting on the extent of elemental mercury adsorption. The highest elemental mercury (Hg°) adsorption capacity was obtained for the CP-CHAR (3142.57 µg g(-1)), which significantly outperformed the pristine and activated carbon adsorbents, as well as higher than some adsorbents reported in the literature.
A new sensing area for a sensor based on surface plasmon resonance (SPR) was fabricated to detect trace amounts of mercury and lead ions. The gold surface used for SPR measurements were modified with polypyrrole-chitosan (PPy-CHI) conducting polymer composite. The polymer layer was deposited on the gold surface by electrodeposition. This optical sensor was used for monitoring toxic metal ions with and without sensitivity enhancement by chitosan in water samples. The higher amounts of resonance angle unit (ΔRU) were obtained for PPy-CHI film due to a specific binding of chitosan with Pb(2+) and Hg(2+) ions. The Pb(2+) ion bind to the polymer films most strongly, and the sensor was more sensitive to Pb(2+) compared to Hg(2+). The concentrations of ions in the parts per million range produced the changes in the SPR angle minimum in the region of 0.03 to 0.07. Data analysis was done by Matlab software using Fresnel formula for multilayer system.
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.
In the present study, ion imprinted polymer monoliths (IIPMs) were developed to overcome the limitations of ion imprinted polymer particles (IIPPs) used for the removal of Hg(II) ions from waste water samples. The adsorbents preparation, characterization and Hg(II) removal were very well reported. The IIPMs on porogen optimization was prepared using the molding technique with Hg(II) as a template ion, [2-(methacryloyloxy)ethyl]trimethylammonium cysteine (MAETC) as ligand, methacrylic acid (MAA) as functional monomer, ethylene glycol dimethacrylamide (EGDMA) as cross-linker, benzoyl peroxide as an initiator and methanol and acetonitrile as porogen in the polypropylene tube (drinking straw) as mold. The IIPMs prepared with higher volumes of porogen were indicated to have a good adsorption rate for the Hg(II) removal along with good water permeability and larger porosity as compared to a lower volume of porogen. The IIPMs prepared using the binary porogen were able to improve the porosity and surface area of the monolithic polymers as compared to the single porogen added IIPMs. Finally, we indicate from our analysis that the IIPM having the efficient capacity for the Hg(II) ions is easy to prepare, and has higher water permeability along with high porosity and high adsorption capacity and all these factors making it one of the suitable adsorbent for the successful removal of Hg(II) ions.
This study applied the use of sequential extraction technique and simple bioaccessibility extraction test to quantify the bioavailable fractions and the human bioaccessible concentration of metals collected from nine stations in surface sediment of the Langat River. The concentrations of total and bioaccessible metals from different stations were in the range of 0.49-1.04, 0.10-0.32 μg g-1 for T-Cd, Bio-Cd, respectively, and 12.9-128.03, 2.06-8.53 μg kg-1 for T-Hg, Bio-Hg, respectively. The results revealed highest R-Bio-Cd in Banting station (55.3 %), while the highest R-Bio-Hg was in Kajang station (49.61 %). The chemical speciation of Cd in most sampling stations was in the order of oxidisable-organic > residual > exchangeable > acid-reducible, while speciation of Hg was in the order of exchangeable > residual > oxidisable-organic > acid-reducible. The correlation matric of mean content showed that the TOM, particle size and Mg++ in polluted surface sediments was highly correlated with total mercury. The PCA showed that the main factors influencing the bioaccessibility of Hg in surface sediments were the sediment TOM, F1 (EFLE) and F3 (oxidation-organic), while the factor influencing the bioaccessibility of Cd was the F3 (oxidation-organic) and T-Cd.
This study is to determine total mercury in edible tissues of eight species of cephalopods and 12 species of crustaceans purchased from 11 identified major fish landing ports and wet markets throughout Peninsular Malaysia. The concentration of mercury was measured by cold vapor atomic absorption spectrometry (AAS) technique using the Perkin Elmer Flow Injection Mercury System (FIMS-400). In general, the mercury levels were low with concentrations in cephalopods ranging from 0.099 to 2.715 mg/kg dry weight (or 0.0184-0.505 mg/kg wet weight) and in crustaceans ranging from 0.057 to 1.359 mg/kg dry weight (or 0.0111-0.265 mg/kg wet weight). The mercury levels showed no significant differences (P > 0.05) between species for both cephalopods and crustaceans. There was no significant correlation between mercury concentrations and the body size of individual for both groups as well. Comparisons with mercury levels obtained found from other previous studies and/or species noted that they were of the same magnitude or relatively low compared to various locations reported worldwide.
In this study, a potentiometric sensor composed of palm shell activated carbon modified with trioctylmethylammonium thiosalicylate (TOMATS) was used for the potentiometric determination of mercury ions in water samples. The proposed potentiometric sensor has good operating characteristics towards Hg (II), including a relatively high selectivity; a Nernstian response to Hg (II) ions in a concentration range of 1.0 × 10(-9) to 1.0 × 10(-2) M, with a detection limit of 1 × 10(-10) M and a slope of 44.08 ± 1.0 mV/decade; and a fast response time (~5 s). No significant changes in electrode potential were observed when the pH was varied over the range of 3-9. Additionally, the proposed electrode was characterized by good selectivity towards Hg (II) and no significant interferences from other cationic or anionic species.
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.
Extraction of protease from a local ginger rhizome (Zingiber officinale var. Bentong) was carried out. The effect of extraction pH (6.4, 6.8, 7.0, 7.2, 7.6, 8.0, 8.4, and 8.8) and stabilizers (0.2% ascorbic acid, 0.2% ascorbic acid and 5 mM EDTA, or 10 mM cysteine and 5 mM EDTA) on protease activity during extraction was examined. pH 7.0 potassium phosphate buffer and 10 mM cysteine in combination with 5 mM EDTA as stabilizer were found to be the most effective conditions. The extraction procedure yielded 0.73% of Bentong ginger protease (BGP) with a specific activity of 24.8±0.2 U/mg protein. Inhibitory tests with some protease inhibitors classified the enzyme as a cysteine protease. The protease showed optimum activity at 60 °C and pH 6-8, respectively. The enzyme was completely inhibited by heavy metal cations such as Cu2+, and Hg2+. SDS stimulated the activity of enzyme, while emulsifiers (Tween 80 and Tween 20) slightly reduced its activity. The kinetic analysis showed that the protease has Km and Vmax values of 0.21 mg mL-1 and 34.48 mg mL-1 min-1, respectively. The dried enzyme retained its activity for 22 months when stored at -20 °C.