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.
The constant increase of heavy metals into the aqueous environment has become a contemporary global issue of concern to government authorities and the public. The study assesses the concentration, distribution, and risk assessment of heavy metals in freshwater from the Linggi River, Negeri Sembilan, Malaysia. Species sensitivity distribution (SSD) was utilised to calculate the cumulative probability distribution of toxicity from heavy metals. The aquatic organism's toxicity data obtained from the ECOTOXicology knowledgebase (ECOTOX) was used to estimate the predictive non-effects concentration (PNEC). The decreasing sequence of hazardous concentration (HC5) was manganese > aluminium > copper > lead > arsenic > cadmium > nickel > zinc > selenium, respectively. The highest heavy metal concentration was iron with a mean value of 45.77 μg L-1, followed by manganese (14.41 μg L-1) and aluminium (11.72 μg L-1). The mean heavy metal pollution index (HPI) value in this study is 11.52, implying low-level heavy metal pollutions in Linggi River. The risk quotient (RQ) approaches were applied to assess the potential risk of heavy metals. The RQ shows a medium risk of aluminium (RQm = 0.1125) and zinc (RQm = 0.1262); a low risk of arsenic (RQm = 0.0122) and manganese (RQm = 0.0687); and a negligible risk of cadmium (RQm = 0.0085), copper (RQm = 0.0054), nickel (RQm = 0.0054), lead (RQm = 0.0016) and selenium (RQm = 0.0012). The output of this study produces comprehensive pollution risk, thus provides insights for the legislators regarding exposure management and mitigation.
Chitosan-magnetic-graphene oxide (CMGO) nanocomposite was prepared for arsenic adsorption. The nanocomposite was characterized through BET, FTIR, FESEM, EDX, and VSM analyses. These characterizations confirmed the formation of CMGO nanocomposites with high specific surface area (152.38 m2/g) and excellent saturation magnetization (49.30 emu/g). Batch adsorption experiments were conducted to evaluate the performance of the nanocomposite in the adsorption of arsenic from aqueous solution. The effects of operational parameters, adsorption kinetic, equilibrium isotherm and thermodynamics were evaluated. The removal efficiency of arsenic increased with increasing adsorbent dosage and contact time. However, the effect of pH followed a different pattern, with the removal efficiency increasing from acidic to neutral pH, and then decreasing at alkaline conditions. The highest adsorption capacity (45 mg/g) and removal efficiency (61%) were obtained at pH 7.3. The adsorption kinetic followed a pseudo-second-order kinetic model. The analysis of adsorption isotherm shows that the adsorption data fitted well to Langmuir isotherm model, indicating a homogeneous process. Thermodynamic analysis shows that the adsorption of As(III) is exothermic and spontaneous. The superparamagnetic properties of the nanocomposite enabled the separation and recovery of the nanoparticles using an external magnetic field. Thus, the developed nanocomposite has a potential for arsenic remediation.
This research was to determine nutritional composition, essential and toxic elemental content, and major phenolic acid with antioxidant activity in Kadsura coccinea fruit. The results indicated that Kadsura coccinea fruit exhibited the high contents of total protein, total fat, ash and essential elements such as calcium (Ca), ferrum (Fe) and phosphorus (P). The levels of four common toxic elements, i.e. cadmium (Cd), mercury (Hg), arsenic (As) and lead (Pb), were lower than legal limits. By high-performance liquid chromatography (HPLC) analysis, gallic acid was identified as major phenolic acid in peel and pulp tissues. Its contents were no significant difference in both tissues. In comparison with two commercial antioxidants, the major phenolic acid extracted from Kadsura coccinea exhibited stronger 1,1-diphenyl-2-picrylhydrazyl radical-scavenging activity and reducing power. Kadsura coccinea fruit is a good source of nutrition and natural antioxidant. It is worthwhile to popularize this exotic fruit around the world.
The first objective of this study was to provide data of arsenic (As) levels in Peninsular Malaysia based on soil samples and accumulation of As in Centella asiatica collected from 12 sampling sites in Peninsular Malaysia. The second objective was to assess the accumulation of As in transplanted C. asiatica between control and semi-polluted or polluted sites. Four sites were selected which were UPM (clean site), Balakong (semi-polluted site), Seri Kembangan (semi-polluted site) and Juru (polluted site). The As concentrations of plant and soil samples were determined by Instrumental Neutron Activation Analysis. The As levels ranged from 9.38 to 57.05 μg/g dw in soils, 0.21 to 4.33 μg/g dw in leaves, 0.18 to 1.83 μg/g dw in stems and 1.32-20.76 μg/g dw in roots. All sampling sites had As levels exceeding the CCME guideline (12 μg/g dw) except for Kelantan, P. Pauh, and Senawang with P. Klang having the highest As in soil (57.05 μg/g dw). In C. asiatica, As accumulation was highest in roots followed by leaves and stems. When the As level in soils were higher, the uptake of As in plants would also be increased. After the transplantation of plants to semi-polluted and polluted sites for 3 weeks, all concentration factors were greater than 50 % of the initial As level. The elimination factor was around 39 % when the plants were transplanted back to the clean sites for 3 weeks. The findings of the present study indicated that the leaves, stems and roots of C. asiatica are ideal biomonitors of As contamination. The present data results the most comprehensive data obtained on As levels in Malaysia.
Colloidal gas aphron dispersions (CGAs) can be described as a system of microbubbles suspended homogenously in a liquid matrix. This work examines the performance of CGAs in comparison to surfactant solutions for washing low levels of arsenic from an iron rich soil. Sodium Dodecyl Sulfate (SDS) and saponin, a biodegradable surfactant, obtained from Sapindus mukorossi or soapnut fruit were used for generating CGAs and solutions for soil washing. Column washing experiments were performed in down-flow and up flow modes at a soil pH of 5 and 6 using varying concentration of SDS and soapnut solutions as well as CGAs. Soapnut CGAs removed more than 70% arsenic while SDS CGAs removed up to 55% arsenic from the soil columns in the soil pH range of 5-6. CGAs and solutions showed comparable performances in all the cases. CGAs were more economical since it contains 35% of air by volume, thereby requiring less surfactant. Micellar solubilization and low pH of soapnut facilitated arsenic desorption from soil column. FT-IR analysis of effluent suggested that soapnut solution did not interact chemically with arsenic thereby facilitating the recovery of soapnut solution by precipitating the arsenic. Damage to soil was minimal arsenic confirmed by metal dissolution from soil surface and SEM micrograph.
Human exposure to arsenic (As) can lead to oxidative stress that can become evident in organs such as the skin, liver, kidneys and lungs. Several intracellular antioxidant defense mechanisms including glutathione (GSH) and metallothionein (MT) have been shown to minimize As cytotoxicity. The current review summarizes the involvement of MT as an intracellular defense mechanism against As cytotoxicity, mostly in blood. Zinc (Zn) and selenium (Se) supplements are also proposed as a possible remediation of As cytotoxicity. In vivo and in vitro studies on As toxicity were reviewed to summarize cytotoxic mechanisms of As. Intracellular antioxidant defense mechanisms of MT are linked in relation to As cytotoxicity. Arsenic uses a different route, compared to major metal MT inducers such as Zn, to enter/exit blood cells. A number of in vivo and in vitro studies showed that upregulated MT biosynthesis in blood components are related to toxic levels of As. Despite the cysteine residues in MT that aid to bind As, MT is not the preferred binding protein for As. Nonetheless, intracellular oxidative stress due to As toxicity can be minimized, if not eliminated, by MT. Thus MT induction by essential metals such as Zn and Se supplementation could be beneficial to fight against As toxicity.
Certain rhizobacteria can be applied to remove arsenic in the environment through bioremediation or phytoremediation. This study determines the minimum inhibitory concentration (MIC) of arsenic on identified rhizobacteria that were isolated from the roots of Ludwigia octovalvis (Jacq.) Raven. The arsenic biosorption capability of the was also analyzed. Among the 10 isolated rhizobacteria, five were Gram-positive (Arthrobacter globiformis, Bacillus megaterium, Bacillus cereus, Bacillus pumilus, and Staphylococcus lentus), and five were Gram-negative (Enterobacter asburiae, Sphingomonas paucimobilis, Pantoea spp., Rhizobium rhizogenes, and Rhizobium radiobacter). R. radiobacter showed the highest MIC of >1,500 mg/L of arsenic. All the rhizobacteria were capable of absorbing arsenic, and S. paucimobilis showed the highest arsenic biosorption capability (146.4 ± 23.4 mg/g dry cell weight). Kinetic rate analysis showed that B. cereus followed the pore diffusion model (R2 = 0.86), E. asburiae followed the pseudo-first-order kinetic model (R2 = 0.99), and R. rhizogenes followed the pseudo-second-order kinetic model (R2 = 0.93). The identified rhizobacteria differ in their mechanism of arsenic biosorption, arsenic biosorption capability, and kinetic models in arsenic biosorption.
Arsenic is a carcinogen element that occurs naturally in our environment. Humans can be exposed to arsenic through ingestion, inhalation, and dermal absorption. However, the most significant exposure pathway is via oral ingestion. Therefore, a comparative cross-sectional study was conducted to determine the local arsenic concentration in drinking water and hair. Then, the prevalence of arsenicosis was evaluated to assess the presence of the disease in the community. The study was conducted in two villages, namely Village AG and Village P, in Perak, Malaysia. Socio-demographic data, water consumption patterns, medical history, and signs and symptoms of arsenic poisoning were obtained using questionnaires. In addition, physical examinations by medical doctors were performed to confirm the signs reported by the respondents. A total of 395 drinking water samples and 639 hair samples were collected from both villages. The samples were analyzed using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) to determine arsenic concentration. The results showed that 41% of water samples from Village AG contained arsenic concentrations of more than 0.01 mg/L. In contrast, none of the water samples from Village P exceeded this level. Whilst, for hair samples, 85 (13.5%) of total respondents had arsenic levels above 1 μg/g. A total of 18 respondents in Village AG had at least one sign of arsenicosis and hair arsenic levels of more than 1 μg/g. Factors significantly associated with increased arsenic levels in hair were female, increasing age, living in Village AG and smoking. The prevalence of arsenicosis in the exposed village indicates chronic arsenic exposure, and immediate mitigation action needs to be taken to ensure the wellbeing of the residents in the exposed village.
Wilting, especially of the leaves, was observed as an initial symptom of arsenate [As(V)] to Ludwigia octovalvis (Jacq.) P. H. Raven. The plants tolerated As(V) levels of 39 mg kg⁻¹ for as long as 35 days of exposure. After 91 days, the maximum concentration of As uptake in the plant occurred at As(V) concentration of 65 mg kg⁻¹ while As concentration in the stems, roots and leaves were 6139.9 ± 829.5, 1284.5 ± 242.9 and 1126.1 ± 117.2 mg kg⁻¹, respectively. In conclusion, As(V) could cause toxic effects in L. octovalvis and the plants could uptake and accumulate As in plant tissues.
The potential of three submerged aquatic plant species (Cabomba piauhyensis, Egeria densa, and Hydrilla verticillata) to be used for As, Al, and Zn phytoremediation was tested. The plants were exposed for 14 days under hydroponic conditions to mine waste water effluents in order to assess the suitability of the aquatic plants to remediate elevated multi-metals concentrations in mine waste water. The results show that the E. densa and H. verticillata are able to accumulate high amount of arsenic (95.2%) and zinc (93.7%) and resulted in a decrease of arsenic and zinc in the ambient water. On the other hand, C. piauhyensis shows remarkable aluminium accumulation in plant biomass (83.8%) compared to the other tested plants. The ability of these plants to accumulate the studied metals and survive throughout the experiment demonstrates the potential of these plants to remediate metal enriched water especially for mine drainage effluent. Among the three tested aquatic plants, H. verticillata was found to be the most applicable (84.5%) and suitable plant species to phytoremediate elevated metals and metalloid in mine related waste water.
This study investigated the contamination levels and sources of As and Cd vicinity area from Nui Phao mine that is one of the largest tungsten (W) open pit mines in the world. Soil and plant samples were collected from the study area to identify the concentrations of As and Cd using aqua-regia or HNO3 digestion. According to the Vietnamese agricultural soil criteria, all soil samples were contaminated with As and Cd. The distribution of As concentration is related to the distance from the Nui Phao mine. The higher As concentrations were measured in the area close to the mine. However, the Cd distribution in the soil showed a different pattern from As. Enrichment factor and Geoaccumulation Index (Igeo) indicated that As in the soil is derived from the mining activities, while Cd could have other geogenic or anthropogenic sources. The ranges of As and Cd concentration in polished rice grains in the Nui Phao mine area exceeded the CODEX criteria (0.2 mg/kg), which indicated extreme contamination. The arsenic concentration between soil and plant samples was determined to be a positive correlation, while the Cd concentration showed a negative correlation, implying that As and Cd have different geochemical behavior based on their sources.
Cockles (Anadara granosa) sample obtained from two rivers in the Penang State of Malaysia were analyzed for the content of arsenic (As) and heavy metals (Cr, Cd, Zn, Cu, Pb, and Hg) using a graphite flame atomic absorption spectrometer (GF-AAS) for Cr, Cd, Zn, Cu, Pb, As and cold vapor atomic absorption spectrometer (CV-AAS) for Hg. The two locations of interest with 20 sampling points of each location were Kuala Juru (Juru River) and Bukit Tambun (Jejawi River). Multivariate statistical techniques such as multivariate analysis of variance (MANOVA) and discriminant analysis (DA) were applied for analyzing the data. MANOVA showed a strong significant difference between the two rivers in term of As and heavy metals contents in cockles. DA gave the best result to identify the relative contribution for all parameters in discriminating (distinguishing) the two rivers. It provided an important data reduction as it used only two parameters (Zn and Cd) affording more than 72% correct assignations. Results indicated that the two rivers were different in terms of As and heavy metal contents in cockle, and the major difference was due to the contribution of Zn and Cd. A positive correlation was found between discriminate functions (DF) and Zn, Cd and Cr, whereas negative correlation was exhibited with other heavy metals. Therefore, DA allowed a reduction in the dimensionality of the data set, delineating a few indicator parameters responsible for large variations in heavy metals and arsenic content. Taking into account of these results, it can be suggested that a continuous monitoring of As and heavy metals in cockles be performed in these two rivers.
Fourteen sediment samples were collected along Linggi River, Malaysia. Neutron activation analysis (NAA) and inductively coupled plasma-mass spectrometry (ICP-MS) techniques were used in the determination of toxic element contents. The results showed that As, Cd and Sb concentrations were higher at all sampling stations, with enrichment factor values ranging from 17.7 to 75.0, 2.1 to 19.5 and 6.6 to 28.4, respectively. Elements of Pb and Zn) were also enriched at most of the sampling stations whilst Cu, Cr and Ni were shown as background levels. The sediment of Linggi River can be categorised as low (<8.0) to very high degree of contamination (>32.0). The mean concentrations of elements viz. Cd, Cr, Ni, Pb, Sb and Zn were lower than the threshold effect level (TEL) of FSQGs values except for As. The concentration of As (arsenic) was higher than PEL and PEC of FSQGs values.
Quantitative indices are classically employed to evaluate the contamination status of metals with reference to the baseline concentrations. The baselines vary considerably across different geographical zones. It is imperative to determine the local geochemical baseline to evaluate the contamination status. No study has been done to establish the background concentrations in tropical rivers of this region. This paper reports the background concentrations of metals in water and sediment of the Baleh River, Sarawak, derived based on the statistical methods where the areas possibly disturbed are distinguished from the undisturbed area. The baseline levels of six elements in water determined were Al (0.34 mg/L), Fe (0.51 mg/L), Mn (0.12 mg/L), Cu (0.01 mg/L), Pb (0.03 mg/L), and Zn (0.05 mg/L). Arsenic and selenium were below the detection limit. For sediment, the background values were established according to statistical methods including (mean + 2σ), iterative 2σ, cumulative distribution frequency, interquartile, and calculation distribution function. The background values derived using the iterative 2σ algorithm and calculated distribution function were relatively lower. The baseline levels calculated were within the range reported in the literatures mainly from tropical and sub-tropical regions. The upper limits proposed for nine elements in sediment were Al (100,879 mg/kg), Cr (75.45 mg/kg), Cu (34.59 mg/kg), Fe (37,823 mg/kg), Mn (793 mg/kg), Ni (22.88 mg/kg), Pb (27.26 mg/kg), Zn (70.64 mg/kg), and Hg (0.33 mg/kg). Quantitative indices calculated suggest low risk of contamination at the Baleh River.
This study was conducted to determine the effects of rice husk ash (RHA) and Fe-coated rice husk ash (Fe-RHA) on the bioavailability and mobility of As, Cd, and Mn in mine tailings. The amendments were added to the tailings at 0, 5, 10, or 20% (w/w) and the mixtures were incubated for 0, 7, 15, 30, 45, and 60 days. The CaCl2 extractable As, Cd, and Mn in the amended tailings were determined at each interval of incubation period. In addition, the tailings mixture was leached with simulated rain water (SRW) every week from 0 day (D 0) until day 60 (D 60). The results showed that both RHA and Fe-RHA application significantly decreased the CaCl2-extractable Cd and Mn but increased that of As in the tailings throughout the incubation period. Consequently, addition of both RHA and Fe-RHA leached out higher amount of As from the tailings but decreased Cd and Mn concentration compared to the controls. The amount of As leached from the Fe-RHA-amended tailings was less than that from RHA-amended tailings. Application of both RHA and Fe-RHA could be an effective way in decreasing the availability of cationic heavy metals (Cd and Mn) in the tailings but these amendments could result in increasing the availability of anionic metalloid (As). Therefore, selection of organic amendments to remediate metal-contaminated tailings must be done with great care because the outcomes might be different among the elements.
The authors describe a method for solvent-free mechano-chemical synthesis of a bioinspired sorbent. A 2D ultra-thin carbon sheet similar to graphene oxide was prepared using a natural waste (onion sheet). The formation of 2D carbon sheets was confirmed by Raman spectroscopy, X-ray photoelectron spectroscopy and ATR-IR. The surface morphology was characterized by field emission scanning electron microscopy and high-resolution tunneling electron microscopy. The carbon sheets were decorated with crystalline MnFe2O4 nanoparticles by solid-state reaction at room temperature. The presence of magnetic particles in the final product was confirmed by vibrating sample magnetometry and electron microscopy. The synergistic effect of carbon sheets and MnFe2O4 led to an enhanced sorption of arsenic species compared to bare carbon sheets or to MnFe2O4 nanoparticles. A column was prepared for the simultaneous preconcentration and determination of trace levels of As(III) and As(V) from water samples. The preconcentration factors are between 900 and 833 for As(III) and As(V) species, respectively. The linearity of the calibration plot ranges from 0.4-10 ng mL-1. The detection limits (at 3σ) for both As(III) and As(V) are 30 pg mL-1. The Student's t values for the analysis of spiked samples are lower than the critical Student's t values at a 95% confidence level. The recoveries from spiked water samples range between 99 and 102.8%. Graphical abstract Schematic representation of the preparation of carbon sheets similar to graphene oxide from onion sheaths after pyrolysis at 800 °C. The prepared carbon sheet-MnFe2O4 composite shows excellent arsenic sorption and preconcentration down to the pg mL-1 concentration.
The ability of non-living biomass of an arsenic-hypertolerant Bacillus cereus strain SZ2 isolated from a gold mining environment to adsorb As (III) from aqueous solution in batch experiments was investigated as a function of contact time, initial As (III) concentration, pH, temperature and biomass dosage. Langmuir model fitted the equilibrium data better in comparison to Freundlich isotherm. The maximum biosorption capacity of the sorbent, as obtained from the Langmuir isotherm, was 153.41 mg/g. The sorption kinetic of As (III) biosorption followed well the pseudo-second-order rate equation. The Fourier transform infrared spectroscopy analysis indicated the involvement of hydroxyl, amide and amine groups in As (III) biosorption process. Field emission scanning electron microscopy-energy dispersive X-ray analysis of the non-living B. cereus SZ2 biomass demonstrated distinct cell morphological changes with significant amounts of As adsorbed onto the cells compared to non-treated cells. Desorption of 94 % As (III) was achieved at acidic pH 1 showing the capability of non-living biomass B. cereus SZ2 as potential biosorbent in removal of As (III) from arsenic-contaminated mining effluent.