Heavy metal pollution is one of the most pervasive environmental problems globally. Novel finely tuned algae have been proposed as a means to improve the efficacy and selectivity of heavy metal biosorption. This article reviews current research on selective algal heavy metal adsorption and critically discusses the performance of novel biosorbents. We emphasize emerging state-of-the-art techniques that customize algae for enhanced performance and selectivity, particularly molecular and chemical extraction techniques as well as nanoparticle (NP) synthesis approaches. The mechanisms and processes for developing novel algal biosorbents are also presented. Finally, we discuss the applications, challenges, and future prospects for modified algae in heavy metal biosorption.
The biosphere is polluted with metals due to burning of fossil fuels, pesticides, fertilizers, and mining. The metals interfere with soil conservations such as contaminating aqueous waste streams and groundwater, and the evidence of this has been recorded since 1900. Heavy metals also impact human health; therefore, the emancipation of the environment from these environmental pollutants is critical. Traditionally, techniques to remove these metals include soil washing, removal, and excavation. Metal-accumulating plants could be utilized to remove these metal pollutants which would be an alternative option that would simultaneously benefit commercially and at the same time clean the environment from these pollutants. Commercial application of pollutant metals includes biofortification, phytomining, phytoremediation, and intercropping. This review discusses about the metal-accumulating plants, mechanism of metal accumulation, enhancement of metal accumulation, potential commercial applications, research trends, and research progress to enhance the metal accumulation, benefits, and limitations of metal accumulators. The review identified that the metal accumulator plants only survive in low or medium polluted environments with heavy metals. Also, more research is required about metal accumulators in terms of genetics, breeding potential, agronomics, and the disease spectrum. Moreover, metal accumulators' ability to uptake metals need to be optimized by enhancing metal transportation, transformation, tolerance to toxicity, and volatilization in the plant. This review would benefit the industries and environment management authorities as it provides up-to-date research information about the metal accumulators, limitation of the technology, and what could be done to improve the metal enhancement in the future.
The concentration of nine trace elements were analyzed in the different tissue organs of commonly available crabs (Portunus sanguinolentus, Portunus pelagicus and Scylla serrate) and bivalve (Polymesoda erosa) species collected from the Miri coast, Borneo in order to evaluate the potential health risk by consumption of these aquatic organisms. Among the analyzed organs, metal accumulation was higher in the gill tissues. The essential (Cu and Zn) and non-essential (Pb and Cd) elements showed the highest (i.e. Zn) and lowest concentrations (i.e. Cd) in their tissue organs, respectively. The estimated daily intake and hazard indices of all metals in the muscle indicate that the measured values were below the provisional tolerable daily intake suggested by the joint FAO/WHO Expert Committee on Food Additives. Compared to Malaysian and international seafood guideline values the results obtained from the present study are lower than the permissible limits and safe for consumption.
Arsenic and 5 heavy metals (nickel, copper, zinc, cadmium and lead) were quantitated in surface water (n = 18) and soil/ore samples (n = 45) collected from 5 land uses (oil palm converted from forest, oil palm in peat swamp, bare land, quarry and forest) in the Selangor River basin by inductively coupled plasma mass spectrometry (ICP-MS). Geographic information system (GIS) was used as a spatial analytical tool to classify 4 land uses (forest, agriculture/peat, urban and bare land) from a satellite image taken by Landsat 8. Source profiling of the 6 elements was conducted to identify their occurrence, their distribution and the pollution source associated with the land use. The concentrations of arsenic, cadmium and lead were also analyzed in maternal blood (n = 99) and cord blood (n = 87) specimens from 136 pregnant women collected at the University of Malaya Medical Center for elucidating maternal exposure as well as maternal-to-fetal transfer. The source profiling identified that nickel and zinc were discharged from sewage and/or industrial effluents, and that lead was discharged from mining sites. Arsenic showed a site-specific pollution in tin-tungsten deposit areas, and the pollution source could be associated with arsenopyrite. The maternal blood levels of arsenic (0.82 ± 0.61 μg/dL), cadmium (0.15 ± 0.2 μg/dL) and lead (2.6 ± 2.1 μg/dL) were not significantly high compared to their acute toxicity levels, but could have attributable risks of chronic toxicity. Those in cord blood were significantly decreased in cadmium (0.06 ± 0.07 μg/dL) and lead (0.99 ± 1.2 μg/dL) but were equivalent in arsenic (0.82 ± 1.1 μg/dL) because of the different kinetics of maternal-to-fetal transfer.
Environmental pollution specifically water pollution is alarming both in the developed and developing countries. Heavy metal contamination of water resources is a critical issue which adversely affects humans, plants and animals. Phytoremediation is a cost-effective remediation technology which able to treat heavy metal polluted sites. This environmental friendly method has been successfully implemented in constructed wetland (CWs) which is able to restore the aquatic biosystem naturally. Nowadays, many aquatic plant species are being investigated to determine their potential and effectiveness for phytoremediation application, especially high growth rate plants i.e. macrophytes. Based on the findings, phytofiltration (rhizofiltration) is the sole method which defined as heavy metals removal from water by aquatic plants. Due to specific morphology and higher growth rate, free-floating plants were more efficient to uptake heavy metals in comparison with submerged and emergent plants. In this review, the potential of wide range of aquatic plant species with main focus on four well known species (hyper-accumulators): Pistia stratiotes, Eicchornia spp., Lemna spp. and Salvinia spp. was investigated. Moreover, we discussed about the history, methods and future prospects in phytoremediation of heavy metals by aquatic plants comprehensively.
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.
Spent Pleurotus sajor-caju compost mixed with livestock excreta, i.e. cow dung or goat manure, was contaminated with landfill leachate and vermiremediated in 75 days. Results showed an extreme decrease of heavy metals, i.e. Cd, Cr and Pb up to 99.81% removal as effect of vermiconversion process employing epigeic earthworms i.e. Lumbricus rubellus. In addition, there were increments of Cu and Zn from 15.01% to 85.63%, which was expected as non-accumulative in L. rubellus and secreted out as contained in vermicompost. This phenomenon is due to dual effects of heavy metal excretion period and mineralisation. Nonetheless, the increments were 50-fold below the limit set by EU and USA compost limits and the Malaysian Recommended Site Screening Levels for Contaminated Land (SSLs). Moreover, the vermicompost C:N ratio range is 20.65-22.93 and it can be an advantageous tool to revitalise insalubrious soil by acting as soil stabiliser or conditioner.
The Anoxybacillus sp. SK 3-4, previously isolated from a hot spring, was screened for its heavy metals resistance (Al(3+), Mn(2+), Cu(2+), Co(2+), Zn(2+), and Ni(2+)) and the strain was found to be most resistant to aluminum. Significant growth of the strain was observed when it was grown in medium containing aluminum (200 mg L(-1)-800 mg L(-1)) with relative growth rates ranging between 77% and 100%. A gene encoding the aluminum resistance protein (accession number: WP_021095658.1) was found in genome of strain SK 3-4, which revealed high sequence identity (>95%) to its homologues from Anoxybacillus species. Sequence comparisons with two functionally characterized aluminum resistance proteins, namely G2alt and ALU1-P, showed 97% and 81% of sequence identity, respectively. Four putative metal binding sites were detected in SK 3-4 aluminum resistance protein and G2alt at same amino acid residue positions of 186, 195, 198, and 201. Strain SK 3-4 was found to be able to remove aluminum from aqueous solution. This study demonstrated that Anoxybacillus sp. SK 3-4 could be applied in the treatment of aluminum contaminated wastewater.
This study examined the concentration of heavy metals in 13 fish species. The results indicated that shellfish species (clams) have the highest metal concentrations, followed by demersal and pelagic fishes. The mean concentration of metals in clams are Zn 88.74 ± 11.98 µg/g, Cu 4.96 ± 1.06 µg/g, Pb 1.22 ± 0.19 µg/g, Cd 0.34 ± 0.04 µg/g dry wt. basis, whereas the same measure in fish tissues was 58.04 ± 18.51, 2.47 ± 1.21, 0.58 ± 0.27 and 0.17 ± 0.08 µg/g dry wt. basis. The concentrations of heavy metals in clams and fish tissues were still lower than the maximum allowable concentrations as suggested by the Malaysian Food Act (1983) and are considered safe for local human consumption.
The microbial breakdown of chitosan, a fishery waste-based material, and its derivative cross-linked chitosans, in both non-contaminated and contaminated conditions was investigated in a laboratory incubation study. Biodegradation of chitosan and cross-linked chitosans was affected by the presence of heavy metals. Zn was more pronounced in inhibiting microbial activity than Cu and Pb. It was estimated that a longer period is required to complete the breakdown of the cross-linked chitosans (up to approximately 100 years) than unmodified chitosan (up to approximately 10 years). The influence of biodegradation on the bioavailable fraction of heavy metals was studied concurrently with the biodegradation trial. It was found that the binding behaviour of chitosan for heavy metals was not affected by the biodegradation process.
Metal ions are one of the essential elements which are extensively involved in many cellular activities. With rapid advancements in genome sequencing techniques, bioinformatics approaches have provided a promising way to extract functional information of a protein directly from its primary structure. Recent findings have suggested that the metal content of an organism can be predicted from its complete genome sequences. Characterizing the biological metal usage of cold-adapted organisms may help to outline a comprehensive understanding of the metal-partnerships between the psychrophile and its adjacent environment. The focus of this study is targeted towards the analysis of the metal composition of a psychrophilic yeast Glaciozyma antarctica PI12 isolated from sea ice of Antarctica. Since the cellular metal content of an organism is usually reflected in the expressed metal-binding proteins, the putative metal-binding sequences from G. antarctica PI12 were identified with respect to their sequence homologies, domain compositions, protein families and cellular distribution. Most of the analyses revealed that the proteome was enriched with zinc, and the content of metal decreased in the order of Zn > Fe > Mg > Mn, Ca > Cu. Upon comparison, it was found that the metal compositions among yeasts were almost identical. These observations suggested that G. antarctica PI12 could have inherited a conserved trend of metal usage similar to modern eukaryotes, despite its geographically isolated habitat.
In February 2013, forty-seven Notched threadfin bream, the Nemipterus peronii, were sampled from the eastern coastal waters of the South China Sea. The concentration of various elements, namely cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), strontium (Sr), manganese (Mn), selenium (Se), Lead (Pb), nickel (Ni), aluminum (Al), arsenic (As), iron (Fe), and Zinc (Zn) were analyzed in the liver, muscle, and kidney organs of the host, as well as in their parasites Hysterothalycium reliquens (nematode) and the Paraphilometroides nemipteri (nematode), using inductively coupled plasma mass spectrometry (ICP-MS). The former group of parasites showed highest accumulation capacity for Cr, Cu, Fe, Mn, Se, Ni, and Zn while the latter group had high accumulation potential of As, Hg, Cd, Al, Pb, and Sr. The divergence in heavy-metal accumulation profiles of both nematodes is linked with the specificity of microhabitats, cuticle morphology, and interspecific competition. The outcome of this study indicates that both parasite models can be used for biomonitoring of metal pollution in marine ecosystems.
Metallothionein (MT) concentrations in gill and liver tissues of Oreochromis mossambicus were determined to assess biological response of fish to levels of some metals. Metal concentrations in gill and liver tissues of O. mossambicus ranged from 0.6 to 2.6 for Cd, 16 to 52 for Zn, 0.5 to 17 for Cu and 2 to 67 for T-Hg (all in μg/g wet weight, except for T-Hg in ng/g wet weight). Accumulation of Cd, Zn, Cu and Hg (μg/g wet weight) in the liver and gills of O. mossambicus were in the order of liver > gills. The concentrations of Cd, Zn, Cu and Hg in fish tissues were correlated with MT content. The increases in MT levels from the reference area Puchong Tengah compared to the polluted area Kampung Seri Kenangan were 3.4- and 3.8-fold for gills and livers, respectively. The results indicate that MT concentrations were tissue-specific, with the highest levels in the liver. Therefore, the liver can act as a tissue indicator in O. mossambicus in the study area.
Perna viridis (P. viridis) has been identified as a good biological indicator in identifying environmental pollution, especially when there are various types of Heavy Metals Accumulations (HMA) inside its tissue. Based on the potential of P. viridis to accumulate heavy metals and the data on its physical properties, this study proffers to determine the relationships between both properties. The similarities of the physical properties are used to mathematical model their relationships, which included the size (length, width, height) and weight (wet and dry) of P. viridis, whilst the heavy metals are focused on concentrations of Pb, Cu, Cr, Cd and Zn. The concentrations of metal elements are detected by using Flame Atomic Adsorption Spectrometry. Results show that the mean concentration of Pb, Cu, Cr, Cd, Zn, length, width, height, wet weight and dry weight are: 1.12 +/- 1.00, 2.36 +/- 1.65, 2.12 +/- 2.74, 0.44 +/- 0.41 and 16.52 +/- 10.64 mg kg(-1) (dry weight), 105.08 +/- 14.35, 41.64 +/- 4.64, 28.75 +/- 3.92 mm, 14.56 +/- 3.30 and 2.37 +/- 0.86 g, respectively. It is also found out that the relationships between the Heavy Metals Concentrations (HMA) and the physical properties can be represented using Multiple Linear Regressions (MLR) models, relating that the HMA of Zinc has affected significantly the physical growth properties of P. viridis.
Crude extract of ChE from the liver of Puntius javanicus was purified using procainamide-sepharyl 6B. S-Butyrylthiocholine iodide (BTC) was selected as the specific synthetic substrate for this assay with the highest maximal velocity and lowest biomolecular constant at 53.49 µmole/min/mg and 0.23 mM, respectively, with catalytic efficiency ratio of 0.23. The optimum parameter was obtained at pH 7.5 and optimal temperature in the range of 25 to 30°C. The effect of different storage condition was assessed where ChE activity was significantly decreased after 9 days of storage at room temperature. However, ChE activity showed no significant difference when stored at 4.0, 0, and -25°C for 15 days. Screening of heavy metals shows that chromium, copper, and mercury strongly inhibited P. javanicus ChE by lowering the activity below 50%, while several pairwise combination of metal ions exhibited synergistic inhibiting effects on the enzyme which is greater than single exposure especially chromium, copper, and mercury. The results showed that P. javanicus ChE has the potential to be used as a biosensor for the detection of metal ions.
Concentrations of the heavy metals copper (Cu), cadmium (Cd), zinc (Zn), lead (Pb) and nickel (Ni) were determined in the liver, gills and muscles of tilapia fish from the Langat River and Engineering Lake, Bangi, Selangor, Malaysia. There were differences in the concentrations of the studied heavy metals between different organs and between sites. In the liver samples, Cu>Zn>Ni>Pb>Cd, and in the gills and muscle, Zn>Ni>Cu>Pb>Cd. Levels of Cu, Cd, Zn and Pb in the liver samples from Engineering Lake were higher than in those from the Langat River, whereas the Ni levels in the liver samples from the Langat River were greater than in those from Engineering Lake. Cd levels in the fish muscle from Engineering Lake were lower than in that from the Langat River. Meanwhile, the Cd, Zn and Pb levels in the fish muscle from the Langat River were lower than in that from Engineering Lake, and the Ni levels were almost the same in the fish muscle samples from the two sites. The health risks associated with Cu, Cd, Zn, Pb and Ni were assessed based on the target hazard quotients. In the Langat River, the risk from Cu is minimal compared to the other studied elements, and the concentrations of Pb and Ni were determined to pose the greatest risk. The maximum allowable fish consumption rates (kg/d) based on Cu in Engineering Lake and the Langat River were 2.27 and 1.51 in December and 2.53 and 1.75 in February, respectively. The Cu concentrations resulted in the highest maximum allowable fish consumption rates compared with the other studied heavy metals, whereas those based on Pb were the lowest. A health risk analysis of the heavy metals measured in the fish muscle samples indicated that the fish can be classified at one of the safest levels for the general population and that there are no possible risks pertaining to tilapia fish consumption.
Livers and muscles of swamp eels (Monopterus albus) were analyzed for bioaccumulation of heavy metals during the plowing stage of a paddy cycle. Results showed heavy metals were bioaccumulated more highly in liver than muscle. Zinc (Zn) was the highest bioaccumulated metal in liver (98.5 ± 8.95 μg/g) and in muscle (48.8 ± 7.17 μg/g). The lowest bioaccumulated metals were cadmium (Cd) in liver (3.44 ± 2.42 μg/g) and copper (Cu) in muscle (0.65 ± 0.20 μg/g). In sediments, Zn was present at the highest mean concentration (52.7 ± 2.85 μg/g), while Cd had the lowest mean concentration (1.04 ± 0.24 μg/g). The biota-sediment accumulation factor (BSAF) for Cu, Zn, Cd and nickel (Ni) in liver tissue was greater than the corresponding BSAF for muscle tissue. For the three plowing stages, metal concentrations were significantly correlated between liver and muscle tissues in all cases, and between sediment and either liver or muscle in most cases. Mean measured metal concentrations in muscle tissue were below the maximum permissible limits established by Malaysian and U.S. governmental agencies, and were therefore regarded as safe for human consumption.
Experiments were conducted to remove heavy metals (Cr, Cd, Pb, Cu and Zn) from urban sewage sludge (SS) amended with spent mushroom compost (SMC) using worms, Lumbricus rubellus, for 105 days, after 21 days of pre-composting. Five combinations of SS/SMC treatments were prepared in triplicate along with a control for each treatment in microcosms. Analysis of the earthworms' multiplication and growth and laboratory analysis were conducted during the tenth and fifteenth week of vermicomposting. Our result showed that the final biomass of earthworms (mg) and final number of earthworms showed significant differences between treatments i.e. F=554.70, P=0.00 and F=729.10, P=0.00 respectively. The heavy metals Cr, Cd and Pb contained in vermicompost were lower than initial concentrations, with 90-98.7 percent removal on week ten. However, concentrations of Cu and Zn, that are considered as micronutrients, were higher than initial concentrations, but they were 10-200-fold lower than the EU and USA biosolid compost limits and Malaysian Recommended Site Screening Levels for Contaminated Land (SSLs). An increment of heavy metals were recorded in vermicompost for all treatments on week fifteen compared to week ten, while concentration of heavy metals in earthworms' tissue were lower compared to vermicompost. Hence, it is suggested that earthworms begin to discharge heavy metals into their surroundings and it was evident that the earthworms' heavy metals excretion period was within the interval of ten to fifteen weeks.
Metallothioneins (MTs) are cysteine-rich metal-binding proteins that are involved in cell growth regulation, transportation of metal ions and detoxification of heavy metals. A mesocarp-specific metallothionein-like gene (MT3-A) promoter was isolated from the oil palm (Elaeis guineensis Jacq). A vector construct containing the MT3-A promoter fused to the β-glucuronidase (GUS) gene in the pCAMBIA 1304 vector was produced and used in Agrobacterium-mediated transformation of tomato. Histochemical GUS assay of different tissues of transgenic tomato showed that the MT3-A promoter only drove GUS expression in the reproductive tissues and organs, including the anther, fruit and seed coat. Competitive RT-PCR and GUS fluorometric assay showed changes in the level of GUS mRNA and enzyme activity in the transgenic tomato (T(0)). No GUS mRNA was found in roots and leaves of transgenic tomato. In contrast, the leaves of transgenic tomato seedlings (T(1)) produced the highest GUS activity when treated with 150 μM Cu(2+) compared to the control (without Cu(2+)). However, Zn(2+) and Fe(2+) treatments did not show GUS expression in the leaves of the transgenic tomato seedlings. Interestingly, the results showed a breaking-off tissue-specific activity of the oil palm MT3-A promoter in T(1) seedlings of tomato when subjected to Cu(2+) ions.
Thirty snakehead fish, Channa micropeltes (Cuvier, 1831) were collected at Lake Kenyir, Malaysia. Muscle, liver, intestine and kidney tissues were removed from each fish and the intestine was opened to reveal cestodes. In order to assess the concentration of heavy metal in the environment, samples of water in the surface layer and sediment were also collected. Tissues were digested and the concentrations of manganese (Mn), zinc (Zn), copper (Cu), cadmium (Cd) and lead (Pb) were analysed by using inductively-coupled plasma mass-spectrometry (ICP-MS) equipment. The results demonstrated that the cestode Senga parva (Fernando and Furtado, 1964) from fish hosts accumulated some heavy metals to a greater extent than the water and some fish tissues, but less than the sediment. In three (Pb, Zn and Mn) of the five elements measured, cestodes accumulated the highest metal concentrations, and in remaining two (Cu and Cd), the second highest metal accumulation was recorded in the cestodes when compared to host tissues. Therefore, the present study indicated that Senga parva accumulated metals and might have potential as a bioindicator of heavy-metal pollution.