Biotechnological advances in bioremediation of heavy metals contaminated ecosystems: an overview with special reference to phytoremediation

The ability of heavy metals bioaccumulation to cause toxicity in biological systems—human, animals, microorganisms and plants—is an important issue for environmental health and safety. Recent biotechnological approaches for bioremediation include biomineralization (mineral synthesis by living organisms or biomaterials), biosorption (dead microbial and renewable agricultural biomass), phytostabilization (immobilization in plant roots), hyperaccumulation (exceptional metal concentration in plant shoots), dendroremediation (growing trees in polluted soils), biostimulation (stimulating living microbial population), rhizoremediation (plant and microbe), mycoremediation (stimulating living fungi/mycelial ultrafiltration), cyanoremediation (stimulating algal mass for remediation) and genoremediation (stimulating gene for remediation process). The adequate restoration of the environment requires cooperation, integration and assimilation of such biotechnological advances along with traditional and ethical wisdom to unravel the mystery of nature in the emerging field of bioremediation. This review highlights better understanding of the problems associated with the toxicity of heavy metals to the contaminated ecosystems and their viable, sustainable and eco-friendly bioremediation technologies, especially the mechanisms of phytoremediation of heavy metals along with some case studies in India and abroad. However, the challenges (biosafety assessment and genetic pollution) involved in adopting the new initiatives for cleaning-up the heavy metals-contaminated ecosystems from both ecological and greener point of view must not be ignored.     

Flocculation of heavy metals during mixing of freshwater with Caspian Sea water

Flocculation of colloidal size fraction for Cu, Zn, Pb, Ni and Mn was investigated on a series of mixtures with water salinities ranging from 1.5 to 9.5‰ during mixing of Haraz River with the Caspian Sea water. The flocculation trend of Zn (85.5%) > Mn (55.2%) > Cu (39.6%) > Pb (33.7%) > Ni (11.3%) indicates that Cu, Zn, Pb and Mn have non-conservative behavior and Ni has relatively conservative behavior during estuarine mixing. Highest flocculation of heavy metals occurs between salinities of 1.5 and 4.5‰. Statistical analysis indicates that the flocculation of Cu, Zn and Ni is governed by pH and total nitrogen.     

Relationship between heavy metals and polycyclic aromatic hydrocarbons in the multi-phases of Nanhu Lake, China

Heavy metals （HMs） and polycyclic aromatic hydrocarbons （PAHs） are two sorts of important pollutants, which were frequently detected in natural aquatic environments at the same time. Surfacial sediments （SSs）, suspended particulates （SPs） and natural surface coatings （NSCs） are recognized as the key solid sinks and sources of heavy metals （HMs） and organic materials （OMs） in natural water systems, playing critical roles in the cycling and transformation of pollutants. The behaviors of HMs in the multi-phases （SSs, SPs and NSCs） have been well investigated, but less reports on those of PAHs, especially on those of HMs and PAHs simultaneously in the multi-phases. Hence, the relationship between HMs （Pb, Cd and Cu） and PAHs （fluorene, phenanthrene, anthracene and pyrene） in the multi-phases of Nanhu Lake in Changchun, China, was studied in this study using methods of acid digestion and extraction, in order to reveal the combined pollution of HMs and PAHs in Nanhu Lake. The information indicated that HMs and PAHs have the similar distribution patterns in the multi-phases of Nanhu Lake, with increasing levels of riMs and PAHs in the SSs, SPs and NSCs. And the enrichment capacities of SPs and NSCs for HMs and PAHs in the water were similar to each other and much greater than that of SSs, implying that SPs and NSCs contributed more to the transference and transformation of HMs and PAHs in the aquatic environments. The relationship between HMs and PAHs has been analyzed by SPSS statistical analysis, and the results showed that the significant correlation of riMs and PAHs was found in the SSs at the confidence level of p = 0.05, but Pb, Cd or Cu had no correlation with any monomer of PAHs in the SPs or NSCs, highlighting the existence of combined pollution of HMs and PAHs in SSs. This was partly due to the relative lability of SPs or NSCs compared to SSs resulting from the water quality of being varied.     

Concentrations of heavy metals and polycyclic aromatic hydrocarbons in river sediments: geochemical background,man's influence and environmental impact

Sediment analysis is used for detecting pollution sources; in addition, sediments are increasingly investigated as a pollution proper and as a carrier and possible source of contaminants in aquatic systems. Amongst the various groups of pollutants which possess a strong affinity to sedimentary materials, heavy metals and polycyclic aromatic hydrocarbons present the greatest environmental hazard. A review is given of pre-civilisational concentrations (“background” values) of both heavy metals and polycyclic aromatic hydrocarbons in fluviatile sediments, and their development during the past 100 years. The impact of sediment associated heavy metal pollution on both biota and water is discussed.     

An integrative approach toward biosensing and bioremediation of metals and metalloids

The contamination of harmful metals and metalloids has emerged as a major issue of concern with the industrial and agricultural progress and increase in human population in the last century. Natural biogeochemical activities are also responsible for increase in the level of elements. Metal(loid)s reach to humans either directly through contaminated drinking water or through the food when crop is cultivated in contaminated areas. Metal(loid)s have carcinogenic, mutagenic, and toxicological properties and hence are a burden to body and the cause of a number of health problems. To combat the menace of metal(loid)s contamination, there is a need to not only precisely monitor their levels in the environment but also to remove them efficiently. In addition, these two basis processes require being a low-cost affair to be affordable for routine operation and for most of the areas and people. Biosensors and bioremediation are two important areas, which offer hope to achieve the goals by allowing sensing of metal(loid)s precisely and removing them at a low cost and in easily operable manner. The present article reviews progress of biosensor and bioremediation approaches and proposes prospective feasible strategies for future.     

Effect of pH and salinity on flocculation process of heavy metals during mixing of Aras River water with Caspian Sea water

The flocculation process of metals can play an effective and important role in self-purification of metals during the mixing of freshwater with seawater in estuary. Such processes are of highly ecological and biological importance. The present study deals with the effect of pH and salinity on the flocculation process of dissolved Cu, Mn, Ni, Zn and Pb on a series of mixtures with salinities ranging from 0.5 to 2.5 ‰ with various pHs values (pH 7, 7.5 and 8) during the mixing of the Aras River water with the Caspian Sea water. The flocculation trend of Pb (100 %) > Ni (62.5 %) > Zn (30.43 %) > Mn (25 %) > Cu (18.18 %) at different salinity regimes (0.5–2.5 ‰) at pH 7, indicates well that Pb, Ni, Zn and Mn have non-conservative behavior and Cu has relatively conservative behavior. At various salinity ranges (0.5–2.5 ‰) and pH 7.5, the flocculation trend of Pb (100 %) > Ni (62.5 %) > Mn (37.5 %) > Cu (24.24 %) > Zn (17.39 %) indicates that Pb, Ni, Mn and Cu have non-conservative behavior and Zn has relatively conservative behavior. Also, the flocculation trend of Pb (100 %) > Zn (78.26 %) > Ni (62.5 %) > Mn (37.5 %) > Cu (15.15 %) at different salinities (0.5–2.5 ‰) and pH 8, indicates that Pb, Zn, Ni and Mn have non-conservative behavior and Cu has relatively conservative behavior. Cluster analysis indicates Mn and Ni are mainly governed by salinity. According to the mean annual discharge of the Aras River (5,323 × 10⁶ m³/year), the annual discharge of dissolved Cu, Mn, Ni, Zn and Pb into the Caspian Sea would reduce from 175.66, 85.17, 85.17, 1,224.29 and 53.23 to 149.04, 53.23, 31.94, 266.15 and 0.00 ton/year, respectively.     

Remediation of ground water containing chlorinated and brominated hydrocarbons, benzene and chromate by sequential treatment using ZVI and GAC

A laboratory experiment with two sequenced columns was performed as a preliminary study for the installation of a permeable reactive barrier (PRB) at a site where a mixed ground water contamination exists. The first column contained granular zero valent iron (ZVI), the second column was filled with granular activated carbon (GAC). Trichloromethane (TCM, 930 μg/l) and chlorobenzene (MCB, 260 μg/l) were added to the ground water from the site as the main contaminants. Smaller amounts (<60 μg/l) of benzene, 1,2-dichloroethane, 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethene (1,1-DCE), trichloroethene (TCE), tetrachloroethene (PCE), 1,2-dichloropropane (1,2-DCP), bromodichloromethane (BDCM), dibromochloromethane (DBCM), tribromomethane (TBM), vinyl chloride and chromate were also added to the water to simulate the complex contamination pattern at the site of interest. PCE, TCE, 1,1-DCE, DBCM, BDCM, TBM, MCB and chromate were remediated in contact with ZVI, while the remaining contaminants showed incomplete degradation. A fraction of 8–16.5% TCM was converted to dichloromethane (DCM). Remaining contaminant concentrations were efficiently sorbed by the GAC until breakthrough of DCM was observed after 1,230 exchanged pore volumes in the GAC. The results show that the complex mixture of contaminants can be remediated by a sequenced PRB consisting of ZVI and GAC and that DCM sorption capacity is the critical parameter for the dimensions of the GAC reactor.     

Competitive sorption of intermixed heavy metals in water repellent soil in Southern Australia

In water repellent soil, Cr, Pb and Cu showed higher adsorption intensities than Zn, Cd and Ni did. Soil water repellency is much more widespread than formerly thought. In order to promote fertility and productivity, the irrigation of recycled water onto water repellent soil may be an applied technology to be used in some areas of Southern Australia. Therefore, heavy metals in recycled water potentially enter into the soil. The competitive sorption and retention capacity of heavy metals in soil are important to be determined, especially considering the special geochemical origin of water repellent soil that was caused by waxes on or between the soil particles. Batch equilibrium sorption experiments on Cd, Cr, Cu, Ni, Pb and Zn in their typical proportion in recycled water were conducted in water repellent soil. The sorption intensity, sorption isotherm in the experiments together showed that Cr, Pb and Cu have higher sorption intensity than those of Zn, Ni and Cd in the competitive system. The risk assessment for the application of recycled water onto water repellent soil is definitely necessary, especially for the metal cations with relatively weak sorption.     

Application of algae in biomonitoring and phytoextraction of heavy metals contamination in urban stream water

Biological technologies for wastewater remediation techniques employed to remove contaminants in urban stream water are increasingly receiving attention worldwide. The purpose of this study was therefore to determine the concentrations of lead, cadmium, copper, zinc, manganese and iron in algal biomass and establish the feasibility of using algae in phytoextraction and bio-monitoring of environmental quality. Analysis of algal biomass samples in the Nakivubo urban stream ecosystem, Kampala, Uganda, showed that there was contamination by lead, cadmium, copper and zinc as indicated by enrichment factor and pollution load index values. It is suspected that industrial and vehicular emissions are the major sources of these pollutants. Calculated bio-concentration factor was >- 1000 but with low concentration thresholds in each element, suggesting that algal biomass was a very good heavy metal accumulator. The bio-concentration values in algal biomass were found to be in the order of copper > zinc > lead > cadmium in the Nakivubo Channelized stream. In conclusion, algae can be a promising aquatic bio-filter plant for phytoextraction and bio-monitoring of polluted urban stream ecosystems and wastewater.     

Pollution of south of Tehran ground waters with heavy metals

The reuse of nutrients and organic matter in wastewater sludge via on agricultural lands application is a desirable goal. However, trace or heavy metals present in sludge pose the risk of human or phytotoxicity from land application. The aim of this research is possibility of ground water pollution of south of Tehran because of ten years irrigation with Ni, Cd and Pb borne waste water. For this purpose, 6 soil samples from southern parts of Tehran city and 2 ones from Zanjan city without lime and organic matter were selected. The soils differed in their texture from sandy to clayey. Each soil sample in duplicate and uniformly packed into PVC columns. Soil samples were irrigated with Cd, Pb and Ni-added wastewater. After irrigating, the columns were cut and the soils separated from sectioned pieces and their heavy metal concentrations (Pb, Cd and Ni) were measured by atomic absorption spectrophotometer by use of HNO₃ 4N solution. Because of high sorption capacity of these elements by soils, these metals were accumulated in surface layer of the soils. Movement in the soils without lime and organic matter were as low as other samples. Ni has had the most accumulation or the least vertical movement, and Pb the opposite ones.     

Characterisation of chlorinated hydrocarbons from chlorine and carbon isotopic compositions: scope of application to environmental problems

A set of chlorinated hydrocarbons (TCE, PCE, DCM, 1,1,1-TCA, chloroform) provided by four manufacturers has been isotopically characterised for both C and Cl, using a new sensitive method. A very large range of δ¹³C (from −51.66 to −24.07‰/PDB) associated with a very large range of δ³⁷Cl (from −2.7 to +3.4‰/SMOC) was obtained. This range of δ³⁷Cl is much larger than that of inorganic Cl (±1‰ SMOC) and most individual solvents show a very distinct δ³⁷Cl compared to inorganic Cl isotopic signatures. Moreover, δ³⁷Cl/δ¹³C pairs are distinct from one solvent/manufacturer to another. In a δ¹³C versus δ³⁷Cl diagram, δ³⁷Cl / δ¹³C pairs show different trends for the products of a single manufacturer compared to another. This suggests that Cl isotopic compositions are probably highly fractionated during organic synthesis. The δ³⁷Cl values can be interpreted in terms of the probable manufacturing processes. Unlike the data published previously, with one exception, all the new results for samples reported here have positive δ³⁷Cl values which might differentiate natural Cl from that derived from degradation. This method has significant potential as a tool for investigating environmental pollution problems; in particular, it offers the possibility for validating models of transport and fate of pollutants.     

Stabilities of heavy metals in soils treated with red mud

This paper discussed the stabilities of heavy metals in soils treated with red mud. Soil has been polluted by heavy metals more and more seriously during recent several decades, and they are harmful to mankind and animals. The current tendency is to develop in-situ technique by using industrial processing waste as additives to stabilized heavy metals to minimize the disturbance of contaminated soils. Soil samples were collected from the Niujiaotang mining area, Guizhou Province, southwestern China. They were farmed soils polluted weakly by fly ash （QBT） and polluted badly by waste water （BXT） from smelter, respectively. One of the red mud samples （BRM） was collected from Bayer process and the other （CRM） from confederate process in the Alumina Plant of Guizhou. Free metal ion concentrations were analyzed with Donnan Membrane Technique and predicted with ECOSAT. The concentrations of free heavy metal ions in QBT increased after appending CRM, but decreased when adding BRM. The more the red mud was added, the higher the concentration would be, and the free concentrations of nickel and cadmium ions would vary more greatly than those of copper and zinc ions. When appending red muds into BXT, the free concentrations of copper and zinc ions varied little. While those of free nickel and cadmium decreased obviously at the ratio of 2.00%. The variation of the concentration was still biggish after appending BRM at the ratio of 0.50%, but smaller than that of 2.00%. The concentrations of free cadmium ions increased after adding CRM at the ratio of 0.50%. All experimental processes were modeled through ECOSAT. The predicted and measured results were consistent, except for zinc. Contributions of soil sorbents to the heavy metal adsorptions were also modeled through ECOSAT. The sorbents in soil included soil organic matter, iron hydroxides, clay and the Donnan gel of soil organic matter. Compared to the soils without red muds, no matter what kind of red mud and how much was added in soil, the contributions changed slightly.     

Health risk of heavy metals from vegetables irrigated with sewage water in peri-urban of Dera Ismail Khan,Pakistan

Health risks of heavy metals in vegetables irrigated with sewage water were investigated in the present study. The findings indicated a massive accumulation of heavy metals in soil and vegetables collected from Dera Ismail khan, Pakistan. The concentration levels of heavy metal in vegetables grown on soil irrigated with untreated sewage water were significantly higher at (P ≤ 0.001) than in vegetables grown on fresh-water-irrigated soil and proceeded the recommended limits of World health organization. Moreover, the findings also indicated that the adults and children consuming such vegetables ingested a large proportion of the selected toxic metals. Health risk index was greater than one for Pb and Cd in all the selected vegetables and was greater than one for Ni in three vegetables like Spinacia oleracea, Benincasa fistulosa and Lactuca sativa. Health risk assessment would be a useful tool for information regarding any threats of heavy metals contamination in vegetables.     

Ecological risk assessment of heavy metals sampled in sediments and water of the Houjing River,Taiwan

The Houjing River flows through Kaohsiung, the most industrialized city in southern Taiwan. In this study, heavy metal concentrations in water and sediments from samples along the river were investigated to illustrate metal contamination levels and call for the awareness of industrial pollution prevention. The heavy metal concentrations in the water samples were low and appear to pose little direct risk to aquatic life and irrigation, but heavy metal concentrations in the sediments are locally very high and present an environmental risk. Cadmium, Cu, and Zn were found in higher concentrations in the river sediments than those recommended in some sediment quality guidelines and findings of river sediments in similar studies worldwide. Hence, the ecological risk of heavy metal contamination in sediments was assessed using the pollution load index (PLI) and potential ecological risk index (RI). Three of the eleven sites sampled were found to have PLI values higher than 1 and 8 of them had ‘considerable’ to ‘very high’ RI values, suggesting a considerable ecological risk. These findings provide an insight into elemental metal contamination of the Houjing River and present a baseline data set, which will be critical for future development and environmental protection plans devised for the region.     

Assessment of atmospheric particulate matter and heavy metals: a critical review

This paper gives detailed comprehensive review of atmospheric assessment of particulate matter and heavy metals. Previous research works executed on this subject matter in the past four decades were adequately scrutinized. Various equipments for assessing atmospheric particulate matter and heavy metals were presented. Mathematical modeling equations for source apportionment and characterization, deposition rate prediction and health risk characterization of PM₁₀ were also presented. However, the following conclusions were made: (1) there is need for improvement on the mathematical models by reducing the number of assumptions made in developing them. (2) Comparative analysis of concentrations of heavy metals in the atmosphere under the same environment for different methodologies should be executed for accuracy purposes. (3) Cost implication of assessing, monitoring and controlling these unfriendly substances should be examined, and hence, involvement of cost engineers may be of immense help. (4) Further research works should be done on Air-Q 2.2.3 model currently identified as a new methodology for provision of quantitative data on the impact of particulate matter exposure on the health of people. (5) Compliance monitoring networks should be designed to ease data collection for the observables, locations and time periods that allowed receptor models to be applied. (6) There is need for much more research works that enable optimal control and regulation of emission of heavy metals into the atmosphere in order to reduce health effects of these inhalable substances.     

Bioaccumulation of heavy metals in organs of fresh water fish Cyprinus carpio (Common carp)

The objective of the present study is to determine the bioaccumulation of heavy metals in various organs of the fresh water fish exposed to heavy metal contaminated water system. The experimental fish was exposed to Cr, Ni, Cd and Pb at sublethal concentrations for periods of 32 days. The elements Cd, Pb, Ni and Cr were assayed using Shimadzu AA 6200 atomic absorption spectrophotometery and the results were given as μ/g dry wt. The accumulation of heavy metal gradually increases in liver during the heavy metal exposure period. All the results were statistically significant at p < 0.001. The order of heavy metal accumulation in the gills and liver was Cd > Pb > Ni > Cr and Pb > Cd > Ni > Cr. Similarly, in case of kidney and flesh tissues, the order was Pb > Cd > Cr > Ni and Pb > Cr > Cd > Ni. In all heavy metals, the bioaccumulation of lead and cadmium proportion was significantly increased in the tissues of Cyprinus carpio (Common carp).     

利用黏土矿物计算背景值评估沉积物重金属污染

综合考虑样品性质及粒度的影响,提出利用黏土矿物计算背景值的方法。实例研究表明,研究区沉积剖面不同深度样品的背景值存在一定的差异。将实测值与背景值之比视为富集因子,发现As、Cr、Cu在剖面的中下部弱富集;Pb在剖面中部弱富集;Zn与Cd在剖面的不同位置的富集程度变化较大,在中部显著富集,表层及底部中度富集。与传统方法相比,该方法综合考虑了粒度和样品性质的影响,并且可以计算出不同位置样品的背景值,使得评估结果更加准确。     

Occurrence of tributyltin compounds and characteristics of heavy metals

Surface sediment samples were collected from Tanzanian major commercial ports and studied for the distribution and behavior of tributyltin (TBT) compounds and heavy metals. The content of TBT in sediments ranged from ND-3670 ng (Sn) g¹dry wt (1780 ± 1720) (Mean ± SD) at Zanzibar and from ND-16700 ng (Sn)g¹ dry wt (4080 ± 7540) at Dar es Salaam ports, respectively. Maximum TBT levels were detected inside the both ports. Metabolic degradation of butyltin compounds (BTCs) showed that MBT + DBT > TBT %, this may be attributed by the warm ambient water and intense sunlight in the tropical regions. A sequential extraction procedure was undertaken to provide detailed chemical characteristics of heavy metals in the sediments. The procedure revealed that about 50% of Fe in the both ports is in immobile fraction (residual fraction) while other metals; Cd, Cu, Ni, Co, Zn, Pb, and Mn were mostly found in exchangeable or carbonate fractions and thus can be easily remobilized and enter the aquatic food chain. This paper provides basic information of TBT compounds contamination and chemical characteristics of heavy metals in the marine ecosystem in Tanzania. To our knowledge, this is the first documentation of Organotin compounds (OTCs) in marine environments in East Africa and suggests the importance of further detailed OTCs studies in other sub-Saharan Africa regions