Hexavalent chromium, emanating primarily from the electroplating industries, can be reduced to the less toxic trivalent variety by several methods, including emulsion liquid membrane (ELM). In this work, studies on the continuous removal of chromium from authentic electroplating wastewater by ELM are reported. The effects of treat ratio, external feed phase, and stripping agent concentration were examined. A mathematical boundary breakage model was used to study the extraction efficiency of chromium through the ELM process. The model representing the prediction of ELM extraction performance for chromium was validated through the comparison between the simulation and experimental results. The result showed the simulation model is found to be in good agreement with the experimental result. Almost 100% of 40 ppm chromium in the external feed phase was extracted within 3 to 5 min using 0.022 M TOMAC as extractant, 1.0 M acidic thiourea in the internal phase, and 1 to 5 of treat ratio. PRACTITIONER POINTS: Hexavalent chromium, emanating primarily from electroplating industries, can be reduced to the less toxic trivalent using ELM process. The developed method was tested for its applicability with predominant species of Cr2 O7 2- in real rinse electroplating wastewater. The extraction efficiency (%) of Cr (VI) was almost 100% for 40 ppm Cr in the external feed phase within 3 to 5 min. The result showed the simulation model is found to be in good agreement with the experimental result.
In this study, a response surface methodology (RSM) approach using central composite design (CCD) was investigated to develop a mathematical model and to optimize the effects of pH, adsorbent amount and temperature related to the hexavalent chromium removal by biosorption on peanut shells (PSh). The highest removal percentage of 30.28% was found by the predicted model under the optimum conditions (pH of 2.11, 0.73 g of PSh and 37.2 °C) for a 100 mg/L initial Cr(VI) concentration, which was very near to the experimental value (29.92%). The PSh was characterized by SEM, EDX, FTIR, BET, XRD analyses. Moreover, a Langmuir isotherm fitted well (R2 = 0.992) with the experimental data, and the maximum adsorption capacity was discovered to be 2.48 and 3.49 mg/g respectively at 25 and 45 °C. Kinetic data were well foreseen by pseudo second order. Thermodynamic study depicted that biosorption of Cr(VI) onto PSh was spontaneous and endothermic. Regeneration of the PSh using NaOH showed a loss <5% in the Cr(VI) removal efficiency up to three recycle runs. In summary, the Cr(VI) removal onto economic, sensitive and selective biosorbent (PSh) was optimized using CCD to study biosorption behaviors.
Chromium (Cr) is used as a mixture to improve strength and corrosion resistance. Milling and welding processes can expose workers to Cr through dermal exposure and inhalation. Cr exposure can be determined by urine testing. The purpose of this study was to analyze the concentration of Cr in urine (UCr) of workers. This study was carried out using a cross-sectional method. Sampling was conducted in the village of Mekarmaju, Bandung, Indonesia. The number of respondents included 30 blacksmiths, and the control group comprised 10 people who were not blacksmiths. Cr6+ exposure was measured using a personal sampling pump placed on the collar of the worker's shirt as a breathing zone and then analyzed using a UV-visible spectrophotometer. UCr was measured with a graphite furnace atomic absorption spectrophotometer. The measured Cr6+ concentration in the exposed working area ranged from 0.03 to 0.63 mg/m3, whereas that in non-exposed area ranged from 0.02 to 0.04 mg/m3. Results showed that 16 out of 30 blacksmiths had a UCr concentration above the biological exposure index (BEI) value, 21 had a higher value than the threshold limit value (TLV), and 22 had hazard index (HI) values > 1, which indicated that Cr has a hazardous potential in the body. The analysis of the exposed and control groups showed a significant difference with a p value of 0.000 for TLV, chronic daily intake, and UCr. These results clearly showed that Cr6+ exposure may harm the health of these workers in the future. The results obtained in this study can be used to promote workers' awareness on the potential health risk caused by Cr6+ exposure in the working environment.
Neodymium-doped polyaniline supported Zn-Al layered double hydroxide (PANI@Nd-LDH) nanocomposite has been prepared via an ex-situ oxidative polymerization process. The as-prepared nanocomposite shows selective fluorescence detection and adsorption of hexavalent chromium Cr(VI) within a short period. The fluorescence intensity of PANI@Nd-LDH decreases linearly with Cr(VI) concentrations ranging from 200 ppb to 1000 ppb with a limit of detection (LOD) of 1.5 nM and a limit of quantification (LOQ) of 96 nM. The sensing mechanism can be ascribed by the inner filter effect of Cr(VI), the intercalation of Cr(VI) within the intergallery region of LDH, and the synergistic affinity of metal ions along with the polymer chain for Cr(VI). The adsorption performance of PANI@Nd-LDH nanocomposite is evaluated for Cr(VI) from wastewaters, which displayed high removal capacity towards Cr(VI) (219 mg/g) as compared on bare Nd-LDH (123 mg/g) and LDH (88 mg/g) respectively. The adsorption of Cr(VI) on PANI@Nd-LDH depends on the pH of the aqueous solution. The adsorption isotherm and kinetics are supported by the Langmuir model and pseudo-second-order model, respectively. Owing to the highly sensitive detection and adsorption of Cr(VI) from aqueous water samples demonstrated the potential application of PANI@Nd-LDH as an excellent environmental probe can be exploited.
Water contamination can be detrimental to the human health due to higher concentration of carcinogenic heavy metals such as chromium (Cr) in the wastewater. Many traditional methods are being employed in wastewater treatment plants for Cr removal to control the environmental impacts. Such methods include ion exchange, coagulation, membrane filtration, and chemical precipitation and microbial degradation. Recent advances in materials science and green chemistry have led to the development of nanomaterial that possess high specific surface areas and multiple functions, making them suitable for removing metals such as Cr from wastewater. Literature shows that the most efficient, effective, clean, and long-lasting approach for removing heavy metals from wastewater involves adsorbing heavy metals onto the surface of nanomaterial. This review assesses the removal methods of Cr from wastewater, advantages and disadvantages of using nanomaterial to remove Cr from wastewater and potential negative impacts on human health. The latest trends and developments in Cr removal strategies using nanomaterial adsorption are also explored in the present review.
The present study investigated the sustainable approach for wastewater treatment using waste algal blooms. The current study investigated the removal of toxic metals namely chromium (Cr), nickel (Ni), and zinc (Zn) from aqueous solutions in batch and column studies using biochar produced by the marine algae Ulva reticulata. SEM/EDX, FTIR, and XRD were used to examine the adsorbents' properties and stability. The removal efficiency of toxic metals in batch operations was investigated by varying the parameters, which included pH, biochar dose, initial metal ion concentration, and contact time. Similarly, in the column study, the removal efficiency of heavy metal ions was investigated by varying bed height, flow rate, and initial metal ion concentration. Response Surface Methodology (Central Composite Design (CCD)) was used to confirm the linearity between the observed and estimated values of the adsorption quantity. The packed bed column demonstrated successful removal rates of 90.38% for Cr, 91.23% for Ni, and 89.92% for Zn heavy metals from aqueous solutions, under a controlled environment. The breakthrough analysis also shows that the Thomas and Adams-Bohart models best fit the regression values, allowing prior breakthroughs in the packed bed column to be predicted. Desorption studies were conducted to understand sorption and elution during different regeneration cycles. Adding 0.3 N sulfuric acid over 40 min resulted in the highest desorption rate of the column and adsorbent used for all three metal ions.
Biosorption ability of date palm empty fruit bunch (DPEFB) was examined for the removal of toxic hexavalent chromium (Cr6+) ions from synthetic wastewater. The pretreated DPEFB biosorbent was studied for its morphology and surface chemistry through Scanning electron microscopy, Energy dispersive elemental analysis and Fourier transform infrared spectroscopy. Effect of biosorption parameters such as pH, biosorbent dosage, contact time, temperature, initial feed concentration and agitation speed on the Cr6+ ions removal efficiency by DPEFB was critically evaluated. The isoelectric point for the DPEFB sorbent was observed at pH 2, above which it was dehydronated to capture the positively charged Cr6+ ions. Batch biosorption studies showed that an optimal chromium removal efficiency of 58.02% was recorded by the DPEFB biosorbent for pH 2, dosage 0.3 g, 100 rpm agitation speed, 120 min contact time, 50 mg/L initial feed concentration and 30 °C operational temperature. Thermodynamic analysis showed that the binding of Cr6+ ions on DPEFB surface was exothermic, stable and favorable at room temperature. Equilibrium behavior of chromium binding on DPEFB was more aligned to Temkin isotherm (R2 = 0.9852) highlighting the indirect interactions between Cr6+ ions and the biosorbent. Kinetic modeling revealed that the biosorption of Cr6+ ions by DPEFB obeyed pseudo-second order model than the pseudo-first order and intra-particle diffusion models. Reusability studies of the DPEFB sorbent showed that NaNO3 was an effective regenerant and the biosorbent can be efficiently reused up to three successive biosorption-desorption cycles for chromium removal. In summary, the results clearly showed that the DPEFB biowaste seems to be an efficient, economic and eco-friendly biosorbent for sustainable removal of toxic hexavalent chromium ions from domestic and industrial wastewater streams.
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.
Statistical analysis of heavy metal concentrations in sediment was studied to understand the interrelationship between different parameters and also to identify probable source component in order to explain the pollution status of selected estuaries. Concentrations of heavy metals (Cu, Zn, Cd, Fe, Pb, Cr, Hg and Mn) were analyzed in sediments from Juru and Jejawi Estuaries in Malaysia with ten sampling points of each estuary. The results of multivariate statistical techniques showed that the two regions have different characteristics in terms of heavy metals selected and indicates that each region receives pollution from different sources. The results also showed that Fe, Mn, Cd, Hg, and Cu are responsible for large spatial variations explaining 51.15% of the total variance, whilst Zn and Pb explain only 18.93 of the total variance. This study illustrates the usefulness of multivariate statistical techniques for evaluation and interpretation of large complex data sets to get better information about the heavy metal concentrations and design of monitoring network.
This study focused on the influence of ultramafic terrains on soil and surface water environmental chemistry in Peninsular Malaysia and in the State of Sabah also in Malaysia. The sampling included 27 soils from four isolated outcrops at Cheroh, Bentong, Bukit Rokan, and Petasih from Peninsular Malaysia and sites near Ranau in Sabah. Water samples were also collected from rivers and subsurface waters interacting with the ultramafic bodies in these study sites. Physico-chemical parameters (including pH, EC, CEC) as well as the concentration of major and trace elements were measured in these soils and waters. Geochemical indices (geoaccumulation index, enrichment factor, and concentration factor) were calculated. Al2O3 and Fe2O3 had relatively high concentrations in the samples. A depletion in MgO, CaO, and Na2O was observed as a result of leaching in tropical climate, and in relation to weathering and pedogenesis processes. Chromium, Ni, and Co were enriched and confirmed by the significant values obtained for Igeo, EF, and CF, which correspond to the extreme levels of contamination for Cr and high to moderate levels of contamination for Ni and Co. The concentrations of Cr, Ni, and Co in surface waters did not reflect the local geochemistry and were within the permissible ranges according to WHO and INWQS standards. Subsurface waters were strongly enriched by these elements and exceeded these standards. The association between Cr and Ni was confirmed by factor analysis. The unexpected enrichment of Cu in an isolated component can be explained by localized mineralization in Sabah.
Welding operations are rarely conducted in an air-conditioned room. However, a company would set its welding operations in an air-conditioned room to maintain the humidity level needed to reduce hydrogen cracks in the specimen being welded. This study intended to assess the exposure to metal elements in the welders' breathing zone and toenail samples. Heavy metal concentration was analysed using inductively coupled plasma mass spectrometry. The lung function test was also conducted and analysed using statistical approaches. Chromium and manganese concentrations in the breathing zone exceeded the permissible exposure limit stipulated by Malaysian regulations. A similar trend was obtained in the concentration of heavy metals in the breathing zone air sampling and in the welders' toenails. Although there was no statistically significant decrease in the lung function of welders, it is suggested that exposure control through engineering and administrative approaches should be considered for workplace safety and health improvement.
With growing population and urbanization, there is an increasing exploitation of natural resources, and this often results to environmental pollution. In this review, the levels of heavy metal in lentic compartments (water, sediment, fishes, and aquatic plants) over the past two decades (1997-2017) have been summarized to evaluate the current pollution status of this ecosystem. In all the compartments, the heavy metals dominated are zinc followed by iron. The major reason could be area mineralogy and lithogenic sources. Enormous quantity of metals like iron in estuarine sediment is a very natural incident due to the permanently reducing condition of organic substances. Contamination of cadmium, lead, and chromium was closely associated with anthropogenic origin. In addition, surrounding land use and atmospheric deposition could have been responsible for substantial pollution. The accumulation of heavy metals in fishes and aquatic plants is the result of time-dependent deposition in lentic ecosystems. Moreover, various potential risk assessment methods for heavy metals were discussed. This review concludes that natural phenomena dominate the accumulation of essential heavy metals in lentic ecosystems compared to anthropogenic sources. Amongst other recent reviews on heavy metals from other parts of the world, the present review is executed in such a way that it explains the presence of heavy metals not only in water environment, but also in the whole of the lentic system comprising sediment, fishes, and aquatic plants.
There is a growing concern about human health of residents living in areas where mining and smelting occur. In order to understand the exposure to the potentially toxic elements (PTEs), we here identify and examine the cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb) and zinc (Zn) in scalp hair of residents living in the mining area (Bayan Obo, n = 76), smelting area (Baotou, n = 57) and a reference area (Hohhot, n = 61). In total, 194 hair samples were collected from the volunteers (men = 87, women = 107) aged 5-77 years old in the three areas. Comparing median PTEs levels between the young and adults, Ni levels were significantly higher in adults living in the smelting area while Cr was highest in adults from the mining area, no significant difference was found for any of the elements in the reference area. From the linear regression model, no significant relationship between PTEs concentration, log10(PTEs), and age was found. The concentrations of Ni, Cd, and Pb in hair were significantly lower in the reference area when compared to both mining and smelting areas. In addition, Cu was significantly higher in the mining area when compared to the smelting area. Factor analysis (FA) indicated that men and women from the smelting area (Baotou) and mining area (Bayan Obo), respectively, had different underlying communality of log10(PTEs), suggesting different sources of these PTEs. Multiple factor analysis quantilized the importance of gender and location when combined with PTEs levels in human hair. The results of this study indicate that people living in mining and/or smelting areas have significantly higher PTEs (Cu, Ni, Cd, and Pb) hair levels compared to reference areas, which may cause adverse health effects. Remediation should therefore be implemented to improve the health of local residents in the mining and smelting areas.
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.
Water from 15 sampling stations in Tasik Chini (Chini Lake), Peninsular Malaysia were sampled for 12 months from September 2004 until August 2005 and analyzed for 11 metals including iron (Fe), aluminum (Al), manganese (Mn), barium (Ba), zinc (Zn), lead (Pb), copper (Cu), cadmium (Cd), nickel (Ni), chromium (Cr) and cobalt (Co). Results showed that the mean (min-max) metal concentrations (in micrograms per liter) in Tasik Chini waters for the 12 months sampling based on 15 sampling stations (in descending order) for Fe, Al, Mn, Ba, Zn, Pb, Cu and Cd were 794.84 (309.33-1609.07), 194.53 (62.37-665.93), 29.16 (16.68-79.85), 22.07 (15.64-29.71), 5.12 (2.224-6.553), 2.36 (1.165-4.240), 0.832 (0.362-1.443) and 0.421 (0.254-0.696) respectively. Concentration for three metals i.e. Ni, Cr and Co were too low and not detected by the graphite furnace Atomic Absorption Spectrophotometry (AAS). Comparison with various water quality standards showed that the mean metals concentration in surface water of Tasik Chini were low and within the range of natural background except for Fe and Al. In general, metal concentrations in Tasik Chini water varied temporally and spatially. The main factors influencing these metal concentrations in the water were the raining season and mining activities. Stations located at Tanjung Jerangking and Melai areas were the most effected due to those factors.
Stainless steel wrought wires used as clasp arms for removable partial dentures in Thailand were compared with those used in some other countries (in the as-received condition) in terms of flexibility, Vickers microhardness and composition. The results showed that there were significant differences (P< or =0.05) among the wires. A Japanese stainless steel wire (SK) was obviously different from the others. It had the lowest proportional limit and microhardness, but its flexibility was almost the same. The chemical composition of each wire was not greatly different. The wires were about 18-20 wt% chromium and 8-9 wt% nickel, except for the SK wire, which had about 12 wt% nickel.
The analysis of total organic carbon (TOC) by the American Public Health Association (APHA) closed-tube reflux colorimetric method requires potassium dichromate (K2Cr2O7), silver sulfate (AgSO4), and mercury (HgSO4) sulfate in addition to large volumes of both reagents and samples. The method relies on the release of oxygen from dichromate on heating which is consumed by carbon associated with organic compounds. The method risks environmental pollution by discharging large amounts of chromium (VI) and silver and mercury sulfates. The present method used potassium monochromate (K2CrO4) to generate the K2Cr2O7 on demand in the first phase. In addition, miniaturizing the procedure to semi microanalysis decreased the consumption of reagents and samples. In the second phase, mercury sulfate was eliminated as part of the digestion mixture through the introduction of sodium bismuthate (NaBiO3) for the removal of chlorides from the sample. The modified method, the potassium monochromate closed-tube colorimetry with sodium bismuthate chloride removal (KMCC-Bi), generates the potassium dichromate on demand and eliminates mercury sulfate. The semi microanalysis procedure leads to a 60% reduction in sample volume and ≈ 33.33 and 60% reduction in monochromate and silver sulfate consumption respectively. The LOD and LOQ were 10.17 and 33.90 mg L-1 for APHA, and 4.95 and 16.95 mg L-1 for KMCC-Bi. Recovery was between 83 to 98% APHA and 92 to 104% KMCC-Bi, while the RSD (%) ranged between 0.8 to 5.0% APHA and 0.00 to 0.62% KMCC-Bi. The method was applied for the UV-Vis spectrometry determination of COD in water and wastewater. Statistics was done by MINITAB 17 or MS Excel 2016. ᅟ Graphical abstract.