This article aims to discuss (1) the incorrect identification of Cr(III) and Cr(VI) binding energies in the Cr 2p XPS (X-ray photoelectron spectroscopy) spectra of the laden adsorbent (the nZVI-BC sample after Cr(VI) adsorption), (2) misconception regarding the Weber-Morris intraparticle diffusion model, and (3) inconsistency between the experiential data and the Thomas adsorption rate constants. The authors hope that our comments are beneficial for other researchers to avoid the undesirable mistakes.
The objective of this study was to evaluate the effects ofNi(II) and Cr(VI) individually and in combination on the simultaneous removal of chemical oxygen demand (COD), nitrogen and metals under a sequencing batch reactor (SBR) operation. Three identical laboratory-scale SBRs were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in a ratio of 1:12:1:2:8 for a cycle time of 24 h until the steady state was achieved. Nickel(II) at increasing concentrations up to 35 mg/L was added to one of the reactors; Cr(VI) at increasing concentrations up to 25 mg/L was added to a second reactor; while a combination of Ni(II) and Cr(VI) in equal concentrations up to 10 mg/L was added to a third reactor. The results demonstrate that both Ni(II) and Cr(VI) exerted a more pronounced inhibitory effect on the removal of ammonia nitrogen (AN) than on COD removal. Synergistic and antagonistic inhibitory effects on the rates of COD and AN removal, respectively, were observed for the 50% Ni(II) and 50% Cr(VI) (w/w) mixture in the concentration range between 10 and 20 mg/L. The simultaneous presence of 50% Ni(II) and 50% Cr(VI) at a concentration of 20 mg/L resulted in system failure.
The Cr(III) sorption experiments onto Kappaphycus alvarezii waste biomass were conducted at different pH values (2-6) under the conditions of initial metal concentration of 10-50 mg/L and the chemical compositions of Cr-Cu and Cr-Cd. The Cr(III) sorption capacities were slightly dependent on pH, and the maximum sorption capacity was 0.86 mg/g at pH 3. The sorption capacities increased with increase in the initial metal concentration, whereas it was suppressed by the presence of Cu(II) and Cd(III) in the solution. The Cr(III) sorption equilibrium was evaluated using Langmuir, Freundlich and BET isotherms. The sorption mechanisms were characterised using scanning electron microscopy and Fourier transform infrared spectroscopy. The main mechanisms were ion exchange coupled with a complexation mechanism. Kappaphycus alvarezii waste biomass represents a potential for Cr(III) ion removal from aqueous solution.
Physical adsorption and photocatalytic reduction of Cr(VI) in magnetic separable beads were investigated. In order to elucidate the kinetics of photocatalytic process, operating parameters such as catalyst dosage and the initial concentration were examined in detail. It was observed that the reduction rate of Cr(VI) increased with an increase in the catalyst loading, as this translated into an increase in the number of available active sites. Critical scrutiny of the percentage of the initial reduction rate versus time at various initial concentration of Cr(VI) revealed that the rate of substrate conversion decreased as the initial concentration increased. The kinetic analysis of the photoreduction showed that the removal of Cr(VI) satisfactory obeyed the pseudo first-order kinetic according to the Langmuir-Hinshelwood (L-H) model and the absorption of Cr(VI) on the magnetic beads surfaces was the controlling step in the entire reduction process. Furthermore, desorption experiments by elution of the loaded gels with sodium hydroxide indicated that the magnetic photocatalyst beads could be reused without significant losses of their initial properties even after 3 adsorption-desorption cycles.
The paper reports on the performance of chromium or/and copper supported on H-ZSM-5(Si/Al = 240) modified with silicon tetrachloride (Cr1.5/SiCl4-Z, Cu1.5/SiCl4-Z and Cr1.0Cu0.5/SiCl4-Z) as catalysts in the combustion of chlorinated VOCs (Cl-VOCs). A reactor operated at a gas hourly space velocity (GHSV) of 32,000 h(-1), a temperature between 100 and 500 degrees C with 2500 ppm of dichloromethane (DCM), trichloromethane (TCM) and trichloroethylene (TCE) is used for activity studies. The deactivation study is conducted at a GHSV of 3800 h(-1), at 400 degrees C for up to 12 h with a feed concentration of 35,000 ppm. Treatment with silicon tetrachloride improves the chemical resistance of H-ZSM-5 against hydrogen chloride. TCM is more reactive compared to DCM but it produces more by-products due to its high chlorine content. The stabilization of TCE is attributed to resonance effects. Water vapor increases the carbon dioxide yield through its role as hydrolysis agent forming reactive carbocations and acting as hydrogen-supplying agent to suppress chlorine-transfer reactions. The deactivation of Cr1.0Cu0.5/SiCl4-Z is mainly due to the chlorination of its metal species, especially with higher Cl/H feed. Coking is limited, particularly with DCM and TCM. In accordance with the Mars-van Krevelen model, the weakening of overall metal reducibility due to chlorination leads to a loss of catalytic activity.
Cement is a common cause of dermatitis. Workers affected are usually those in cement factories and at building construction sites. Cement dermatitis among port-workers is not so commonly reported. This paper describes an outbreak of dermatitis among stevodores at a port handling cement. The cement was imported in bags, and because of breakage, there was much spillage. It was also hot and dusty inside the hatch of the ship, and some of the stevodores worked bare-bodied. Cases of dermatitis began to appear in January 1983 and reached a peak in April 1983, gradually subsiding over the next few months to August 1983. This coincided with the increased tonnage of cement handled at the port. A total of 33 stevodores were reported as having dermatitis over this period. Of the 15 cases examined, 13 had eczema, and in 19 the hands and wrists were affected. However, most of the cases had multiple site involvement, including the arms, legs and abdomen.
Samples of cement showed the presence of water-soluble chromium, varying from 9.9 to 17.8pg/g. As the stevodores were reluctant to go for skin patch-testing, only four were tested, but two did not return for the reading of the results. The other two were found to have a positive reaction to dichromates. The outbreak of dermatitis was probably due to several factors which are discussed.
The aqueous extract of various plants like Coriandrum sativum (AECS), Alternanthera tenella colla (AEAT), Spermacoce hispida (AESH) and Mollugo verticillata (AEMV) was studied for its hexavalent chromium (CrVI) reduction property. Even though antioxidant activity was present, AEAT, AESH and AEMV did not reduce CrVI. AECS showed rapid and dose-dependent CrVI reduction. The efficient reduction of 50 mg/L of CrVI using AECS was attained in the presence of 250 µg/mL of starting plant material, incubating the reaction mixture at pH 2, 30°C and agitation at 190 rpm. Under such conditions, about 40 mg/L of CrVI was reduced at 3 h of incubation. FT-IR analysis revealed the involvement of phenols, alcohols, alpha-hydroxy acid and flavonoids present in the AECS for the CrVI reduction. These results indicate that not all the plant extracts with rich antioxidants are capable of reducing CrVI. Using the conditions standardized in the present study, AECS reduced about 80% of CrVI present in the tannery effluent. These results signify the application of AECS as an eco-friendly method in the wastewater treatment.
In this study, effect of degree of deacetylation on property and adsorption capacity of chitosan/polyvinyl Alcohol electrospun membrane has been investigated. Resulting nanofibers were characterized by FESEM, FTIR, XRD, TGA, tensile testing, weight loss test and adsorption test. FESEM result shows, finer nanofiber was fabricated from 42h hydrolyzed chitosan and PVA blend solution. FTIR and XRD result showed a strong interaction between chitosan and polyvinyl alcohol. Higher tensile strength was observed for the nanofiber having 42h hydrolyzed chitosan. Blend solution of chitosan/PVA having low DD chitosan had higher viscosity. The nanofibrous membrane was stable in distilled water, acidic and basic medium. The isotherm study shows that the adsorption capacity (qm) of nanofiber containing higher DD chitosan was higher for Cr(VI). In contrary, the membrane containing chitosan with lower DD showed the higher adsorption capacity for Fe(III) and methyl orange. Moreover, the effect of DD on removal percentage of adsorbate was dependent on the initial concentration of the adsorbate.
In this study, the synthesis and experimental theoretical evaluation of a new chitosan/alginate/hydrozyapatite nanocomposite doped with Mn2 and Fe2O3 for Cr removal was reported. The physicochemical properties of the obtained materials were analyzed using the following methods: SEM-EDX, XRD, FTIR, XPS, pH drift measurements, and thermal analysis. The adsorption properties were estimated based on equilibrium and adsorption kinetics measurements. The Langmuir, Freundlich and Temkin isotherms were applied to analyze the equilibrium data. The thermodynamic analysis of adsorption isotherms was performed. A number of equations and kinetic models were used to describe the adsorption rate data, including pseudo-first (PFOE) and pseudo-second (PSOE) order kinetic equations. The obtained test results show that the synthesized biomaterial, compared to pure chitosan, is characterized by greater resistance to high temperatures. Moreover, this biomaterial had excellent adsorption properties. For the adsorption of Cr (VI), the equilibrium state was reached after 120 min, and the sorption capacity was 455.9 mg/g. In addition, DFT calculations and NCI analyses were performed to get more light on the adsorption mechanism of Cr (VI) on the prepared biocomposite.
Rice is a predominant staple food in many countries. It is a great source of energy but can also accumulate toxic and trace metal(loid)s from the environment and pose serious health hazards to consumers if overdosed. This study aims to determine the concentration of toxic metal(loid)s [arsenic (As), cadmium (Cd), nickel (Ni)] and essential metal(loid)s [iron (Fe), selenium (Se), copper (Cu), chromium (Cr), cobalt (Co)] in various types of commercially available rice (basmati, glutinous, brown, local whites, and fragrant rice) in Malaysia, and to assess the potential human health risk. Rice samples were digested following the USEPA 3050B acid digestion method and the concentrations of metal(loid)s were analyzed using an inductively coupled plasma mass spectrometry (ICP-MS). Mean concentrations (mg/kg as dry weight) of metal(loid)s (n=45) across all rice types were found in the order of Fe (41.37)>Cu (6.51)>Cr (1.91)>Ni (0.38)>As (0.35)>Se (0.07)>Cd (0.03)>Co (0.02). Thirty-three percent and none of the rice samples surpassed, respectively, the FAO/WHO recommended limits of As and Cd. This study revealed that rice could be a primary exposure pathway to toxic metal(loid)s, leading to either noncarcinogenic or carcinogenic health problems. The non-carcinogenic health risk was mainly associated with As which contributed 63% to the hazard index followed by Cr (34%), Cd (2%), and Ni (1%). The carcinogenic risk to adults was high (>10-4) for As, Cr, Cd, and Ni. The cancer risk (CR) for each element was 5 to 8 times higher than the upper limit of cancer risk for an environmental carcinogen (<10-4). The findings from this study could provide the metal(loid)s pollution status of various types of rice which are beneficial to relevant authorities in addressing food safety and security-related issues.
Chromium (Cr) is one of the hazardous heavy metals that is naturally carcinogenic and causes various health problems. Metallic nanoparticles such as silver and copper nanoparticles (Ag NPs and Cu NPs) have gained great attention because of their unique chemical, physical, and biological attributes, serving diverse and significant role in various useful and sustainable applications. In the present study, both of these NPs were synthesized by green method in which Azadirachta indica plant extract was used. These nanoparticles were characterized by using advanced instrumental techniques such as Fourier transmission infrared (FTIR), X-ray diffraction (XRD), scanning electron microscope attached with energy-dispersive spectroscopy (SEM-EDS), and elemental mapping. These environmentally friendly nanoparticles were utilized for the batch removal of Cr from the wastewater. For analysis of adsorption behaviour, a range of kinetic isotherm models (Freundlich, Temkin, Dubinin, and Langmuir) and kinetic models (pseudo-first-order and pseudo-second-order) were used for the Cu-NPs and Ag-NPs. Cu NPs exhibited the highest Cr removal efficiency (96%) within a contact time of 10-15 min, closely followed by Ag NPs which achieved a removal efficiency of 94% under the similar conditions. These optimal outcomes were observed at a sorbent dose of 0.5 g/L for Ag NPs and 0.7 g/L for Cu NPs. After effectively capturing Cr using these nanoparticles, the sorbates were examined through SEM-EDX analysis to observe how much Cr metal was attached to the nanoparticles, potentially for future use. The analysis found that Ag-NPs captured 18% of Cr, while Cu-NPs captured 12% from the aqueous solution. More precise experimental conditions are needed for higher Cr removal from wastewater and determination of the best conditions for industrial-level Cr reuse. Although nanomaterial exhibit high efficiency and selectivity for Cr removal and recovery from wastewater, more research is necessary to optimize their synthesis and performance for industrial-scale applications and develop efficient methods for Cr removal and recovery.
Replacing a single missing anterior tooth can be a challenge. Many factors need to be considered when choosing the appropriate treatment. Several treatment options are well established. This case report is to present the use of a cast cobalt chrome partial denture with custom made porcelain tooth to improve aesthetic. The overall shade of the artificial tooth were nicely matched with the adjacent teeth and definite enamel translucency could be achieved which would not be possible with acrylic or even with readymade porcelain tooth.
Fibre-rich manure derived from grass-fed cattle showed significantly higher intrinsic sorption efficiency on Cr(VI) solution as compared to corncob, sawdust and cogon grass. This observation could be attributed to the ligneous nature and rough surface morphology of the cattle manure. Four-factor, three-level, face-centred composite design (FCCD) suggested the process was greatly affected by initial pH of the solution, contact time and sorbent dosage (p50% adsorption efficiency. It is predicted that both physisorption and chemisorption are involved in the sorption process.
Diplotaxis tenuifolia is a medicinally important perennial plant species, distributed widely alongside the roads in Turkey. The samples were collected from 54 sites, including highways, sideways, industrial areas, urban centres and rural environs. Both the plant and soil samples were analysed to determine the concentrations of different metals using AAS. The results showed that in the soil samples copper and lead were highest near highway 45.533 and 2.865 mg/kg, respectively; but lowest values of copper were determined around industrial areas (3.514 mg/kg), latter however showed higher concentrations of cadmium (0.726 mg/kg) and iron (82.766 mg/kg). The lead as well as iron were the lowest around sideways 1.917 mg/kg and 54.073 mg/kg, respectively, whereas chromium concentrations in the soils were highest near sideways (18.397 mg/kg) and lowest around industrial areas (0.182 mg/kg). The sideways showed very low nickel concentrations (0.271 mg/kg), as compared to the rural areas which had higher nickel concentrations (0.726 mg/kg). No cadmium was detected in the urban soil samples. In the plants copper and chromium were higher in the urban areas 50.130 and 0.238 mg/kg, respectively. The former was lowest around sideways (32.377 mg/kg) and latter around highways (0.114 mg/kg). Both nickel and cadmium were higher in the samples from industrial areas 0.238 and 0.016 mg/kg, respectively. Their values around the highways were lowest 0.182 and 0.005 mg/kg. The samples from urban sites revealed highest values of lead (3.474 mg/kg) and iron (61.304 mg/kg), but the values of lead were lowest around sideways (2.420 mg/kg) and those of iron in the vicinity of industrial areas (20.600 mg/kg). All these findings depict that there is some aerial deposition of these metals on the leaves. A significant correlation is seen between the plants and the soils.
The sorption characteristics of Cr(VI) and Cu(II) by ethylenediamine modified rice hull from single and binary metal ion solutions were evaluated under various experimental conditions. Optimal Cr(VI) and Cu(II) removal from single metal ion solutions occurred at pH 2.0 and 5.5, respectively. Simultaneous removal of Cr(VI) and Cu(II) occurred at pH greater than 3.0. The sorption kinetics of Cr(VI) and Cu(II) from single and binary metal ion solutions were studied with reference to metal concentration, agitation rate and particle size. Sorption of Cr(VI) was more rapid than Cu(II). The kinetics of metal ion sorption fitted a pseudo-second order expression. The variation in the initial uptake rates was very small at an agitation rate beyond 150 rpm and sorption was generally independent of particle size. Equilibrium sorption data could be fitted into the Langmuir isotherm equation. Maximum sorption capacities of ethylenediamine modified rice hull for Cr(VI) at pH 2 and Cu(II) at pH 4 in single metal solutions were 0.45 and 0.06 mmol g(-1), respectively. This corresponds to an enhancement factor of 2.6 and 3 fold for Cr(VI) and Cu(II), respectively, compared to natural rice hull. A synergistic effect was observed for sorption of these ions in binary metal solutions.
The effluent discharge treatment for controlling the environment from non biodegradable metal contaminants using plant extract is an efficient technique. The reduction of hexavalent chromium by abundantly available weed, Aerva lanata L. was investigated using batch equilibrium technique. The variables studied were Cr(VI) concentration, Aerva lanata L. dose, contact time, pH, temperature and agitation speed. Cyclic voltammetry and ICP-MS analysis confirmed the reduction of Cr(VI) to Cr(III). Electrochemical analysis proved that, the chromium has not been degraded and the valency of the chromium has only been changed. ICP-MS analysis shows that 100ng/L of hexavalent chromium was reduced to 97.01ng/L trivalent chromium. These results suggest that components present in the Aerva lanata L. are responsible for the reduction of Cr(VI) to Cr(III). The prime components ferulic acid, kaempherol and β-carboline present in the Aerva lanata L. may be responsible for the reduction of Cr(VI) as evident from LC-MS analysis.
In this study magnetic separable photocatalyst beads containing maghemite nanoparticles (γ-Fe(2)O(3)) in polyvinyl alcohol (PVA) polymer were prepared and used in the reduction of Cr(VI) to Cr(III) in an aqueous solution under sunlight. The unique superparamagnetic property of the photocatalyst contributed by the γ-Fe(2)O(3) and robust property of PVA polymer allow the magnetic beads to be recovered easily and reused for at least 7 times without washing. The concentration of γ-Fe(2)O(3) was varied from 8% (v/v) to 27% (v/v) and the results revealed that the beads with 8% (v/v) γ-Fe(2)O(3) exhibited the best performance where Cr(VI) was reduced to Cr(III) in only 30 min under sunlight. The use of the PVA has improved the bead properties and life cycle of beads which is in line with sustainable practices.
The potential use of non-viable biomass of a Gram negative bacterium i.e. Acinetobacter haemolyticus to remove Cr(III) species from aqueous environment was investigated. Highest Cr(III) removal of 198.80 mg g(-1) was obtained at pH 5, biomass dosage of 15 mg cell dry weight, initial Cr(III) of 100 mg L(-1) and 30 min of contact time. The Langmuir and Freundlich models fit the experimental data (R(2)>0.95) while the kinetic data was best described using the pseudo second-order kinetic model (R(2)>0.99). Cr(III) was successfully recovered from the bacterial biomass using either 1M of CH(3)COOH, HNO(3) or H(2)SO(4) with 90% recovery. TEM and FTIR suggested the involvement of amine, carboxyl, hydroxyl and phosphate groups during the biosorption of Cr(III) onto the cell surface of A. haemolyticus. A. haemolyticus was also capable to remove 79.87 mg g(-1) Cr(III) (around 22.75%) from raw leather tanning wastewater. This study demonstrates the potential of using A. haemolyticus as biosorbent to remove Cr(III) from both synthetic and industrial wastewater.
The present study investigated the biosorption capacity of live and dead cells of a novel Bacillus strain for chromium. The optimum biosorption condition was evaluated in various analytical parameters, including initial concentration of chromium, pH, and contact time. The Langmuir isotherm model showed an enhanced fit to the equilibrium data. Live and dead biomasses followed the monolayer biosorption of the active surface sites. The maximum biosorption capacity was 20.35 mg/g at 25 °C, with pH 3 and contact time of 50 min. Strain 139SI was an excellent host to the hexavalent chromium. The biosorption kinetics of chromium in the dead and live cells of Bacillus salmalaya (B. salmalaya) 139SI followed the pseudo second-order mechanism. Scanning electron microscopy and fourier transform infrared indicated significant influence of the dead cells on the biosorption of chromium based on cell morphological changes. Approximately 92% and 70% desorption efficiencies were achieved using dead and live cells, respectively. These findings demonstrated the high sorption capacity of dead biomasses of B. salmalaya 139SI in the biosorption process. Thermodynamic evaluation (ΔG⁰, ΔH⁰, and ΔS⁰) indicated that the mechanism of Cr(VI) adsorption is endothermic; that is, chemisorption. Results indicated that chromium accumulation occurred in the cell wall of B. salmalaya 139SI rather than intracellular accumulation.