Simultaneous heavy metal removal mechanism by dead macrophytes

The use of dead, dried aquatic plants, for water removal of metals derived from industrial activities as a simple biosorbent material has been increasing in the last years. The mechanism of simultaneous metal removal (Cd2+, Ni2+, Cu2+, Zn2+ and Pb2+) by 3 macrophytes biomass (Spirodela intermedia, Lemna minor and Pistia stratiotes) was investigated. L. minor biomass presented the highest mean removal percentage and P. stratiotes the lowest for all metals tested. Pb2+ and Cd2+ were more efficiently removed by the three of them. The simultaneous metal sorption data were analysed according to Langmuir and Freundlich isotherms. Data fitted the Langmuir model only for Ni and Cd, but Freundlich isotherm for all metals tested, as it was expected. The K(F) values showed that Pb was the metal more efficiently removed from water solution. The adsorption process for the three species studied followed first order kinetics. The mechanism involved in biosorption resulted ion exchange between monovalent metals as counter ions present in the macrophytes biomass and heavy metal ions and protons taken up from water. No significant differences were observed in the metal exchange amounts while using multi-metal or individual metal solutions.     

Biosorption of cadmium and copper contaminated water by Scenedesmus abundans

Experiments were conducted comparing the individual removals of cadmium and copper from water via biosorption using Scenedesmus abundans, a common green algae, to removal in a multi-component system to determine competitive effects, if any, between the metals. The goal was to characterize the biological treatment of water contaminated with heavy metals using live aquatic species. In addition, experiments were performed to measure cell viability as a function of metal concentration and also to compare metal removal using living species to that using nonliving ones. It was shown that, while both living and nonliving S. abundans removed cadmium and copper from water, living algae significantly outperformed nonliving algae. Further, in characterizing biosorption by three concentrations of live S. abundans, capacity curves were created comparing the metal biosorbed per mass algae to the initial metal concentration in solution. The algae concentration was not a factor in the biosorption of either metal individually, such that the capacity of the algae for the metal increased with decreasing algae concentration. At the lowest algae concentration considered, competitive effects were observed at copper and cadmium concentrations above 4 mg/l each. At the highest algae concentration considered, no competitive effects were observed in the range of cadmium and copper concentrations studied (1-7 mg/l). It was concluded that biological treatment of heavy metal contaminated water is possible and that at adequately high algae concentrations, multi-component metal systems can be remediated to the same level as individual metals.     

Metal accumulation in aquatic macrophytes from southeast Queensland,Australia

To determine the extent of metal accumulation in some aquatic macrophytes from contaminated urban streams in southeast Queensland, plants were sampled from six sites, along with contiguous sediments. In all, 15 different species were collected, the most common genera being Typha (Cattails or Bulrushes) and Persicaria (Knotweeds). Before heavy metal analysis, plants were further separated into various morphological tissues, and five selected samples were separated into various physiological tissues. The cadmium, copper, lead and zinc content of the plants were analysed using flames AAS. In general, plant roots exhibited higher metal concentrations than the contiguous sediments. Of the metals of interest, only for zinc was there a relatively clear pattern of increasing accumulation in aquatic macrophytes with increasing sediment metal concentrations. Comparison between morphological tissues of the sampled plants found that roots consistently presented higher metal concentrations than either the stems or leaves, however unlike previous studies, this investigation revealed no consistent trend of stems accumulating more metals than the leaves. For Typha spp., metal concentrations followed the order of roots > rhizomes > leaves, while for Persicaria spp. the order was roots > leaves > stems. The submerged species Myriophyllum aquaticum accumulated the highest levels of metals overall (e.g. Zn 4300 micrograms g-1 dry weight and Cd 6.5 micrograms g-1), and the emergent macrophytes also exhibited relatively high metal contents in their roots. The leaves of the submerged and floating-leafed species collected contained relatively high quantities of the four metals of interest, compared with the leaves of emergent aquatic macrophytes. In the Typha rhizome and Persicaria stem samples analysed for internal variation in metal content, there was a pattern of increasing metal concentrations towards the external sections of the stem, both for subterranean stems (rhizomes) and above-substrate stems. For Persicaria stems, no clear pattern was observed for cadmium and lead, the two metals investigated that are not required by plants for survival.     

Physico-chemical characteristics and pollution level of Lake Nainital (U.P., India): role of macrophytes and phytoplankton in biomonitoring and phytoremediation of toxic metal ions

Lake Nainital is the sole source of drinking water for the local people and even to majority of tourists. In background of lake utility and its importance at national level, such study is essential which is focused on toxic metal pollution and current nutrient status of the lake and their magnification by algae and macrophytes. Study has shown that lake water is rich in nutrients which supports growth of many aquatic macrophytes and algal blooms. Besides, water is contaminated with metals like Cr, Cu, Fe, Mn, Ni, Pb and Zn. Concentration of some of them like Fe, Pb and Ni were higher than the recommended maximum permissible limits. Concentration of these metals were also found high in lake sediments. The level of metals amongst various components of lake varied considerably in different season. Plants and algae growing therein accumulated appreciable amount of metals and water roots of Salix being more efficient than others. High metal removing potential of these plants may be significant for biomonitoring studies and could be a useful phytoremediation technology to restore water quality by harvesting submerged and floating biomass inhabiting littoral zone of the lake.     

Accumulation of nutrients and heavy metals in Phragmites australis (Cav.) Trin. ex Steudel and Bolboschoenus maritimus (L.) Palla in a constructed wetland of the Venice lagoon watershed

A recently constructed wetland, located in the Venice lagoon watershed, was monitored to investigate growth dynamics, nutrient and heavy metal shoot accumulation of the two dominating macrophytes: Phragmites australis and Bolboschoenus maritimus. Investigations were conducted over a vegetative season at three locations with different distance to the inlet point to assess effects on vegetation. The distance from the inlet did not affect either shoot biomass or nutrients (N, P, K and Na) and heavy metals (Cr, Ni, Cu and Zn) shoot content. With the exception of Na, nutrient and heavy metal concentrations were higher in shoots of P. australis than in B. maritimus. Heavy metal concentration in the incoming water and in the soil was not correlated to the plant content of either species. Shoot heavy metal concentrations were similar to those reported in the current literature, but accumulation generally increased towards the end of the growing season.     

Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter

The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted > 99% of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH < 3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology.     

Concentrations of lead in aquatic macrophytes from Shoal Lake, Manitoba, Canada

The ability of aquatic macrophytes to accumulate lead was examined in the context of sample site, sample date, depth, organ and species. Considerable variations in lead concentrations were found between the 11 species of macrophytes studied. The mean lead concentration for all species sampled was 16 microg/g (dry weight) ranging from 0-78 microg/g. Analysis of variance indicated that there were significant differences in the mean lead content of macrophytes collected from different sample sites. Similarly, significantly higher values were observed for plants collected from the upper 2m of water. Seasonal trends in lead accumulation were not observed for Shoal Lake macrophytes.     

Cadmium and chromium removal kinetics from solution by two aquatic macrophytes

The aim of this work was to determine chromium and cadmium bioaccumulation processes of two free-floating macrophytes commonly used in wetlands for water treatment: Salvinia herzogii and Pistia stratiotes. Metal removal from the solution involves two stages: a fast one and a slow one. The fast stage of the Cd uptake is significantly different for each species, while it is not significantly different in Cr uptake. The most important processes of Cd uptake are biological ones in S. herzogii and adsorption, chelation and ionic exchange are in P. stratiotes. The main processes of Cr uptake in both macrophytes are adsorption, chelation and ion exchange. The slow stage is different for each species and metal. Cr precipitation induced by roots occurs in P. stratiotes. Cr uptake through leaves is probably the main cause of the increase of Cr in the aerial parts of S. herzogii.     

Metal accumulation by submerged macrophytes in eutrophic lakes at the watershed scale

Metal concentrations (Al, Ba, Ca, K, Li, Mg, Na, Se, Sr and Ti) in submerged macrophytes and corresponding water and sediments were studied in 24 eutrophic lakes along the middle and lower reaches of the Yangtze River (China). Results showed that these eutrophic lakes have high metal concentrations in both water and sediments because of human activities. Average concentrations of Al and Na in tissues of submerged macrophytes were very high in sampled eutrophic lakes. By comparison, Ceratophyllum demersum and Najas marina accumulated more metals (e.g. Ba, Ca, K, Mg, Na, Sr and Ti). Strong positive correlations were found between metal concentrations in tissues of submerged macrophytes, probably because of co-accumulation of metals. The concentrations of Li, Mg, Na and Sr in tissues of submerged macrophytes significantly correlated with their corresponding water values, but not sediment values.     

Tolerance and uptake of heavy metals by Trichoderma atroviride isolated from sludge

A strain of Trichoderma atroviride, isolated from sewage sludge obtained from a water treatment plant located in Madrid (Spain), has been studied for tolerance to heavy metals (copper, zinc and cadmium) and for its capacities to uptake these metals. It was found that this fungus is capable of surviving high metal concentrations, apparently as a result of the natural selection of resistant cells. Also, growth and metal uptake have been assayed in samples where the fungus was cultured in the presence of a single metal and in the presence of a combination of two or three cations, where additive and synergistic interactions were observed. Finally, metal uptake by this strain has been studied under different nutritional conditions. It was found that the highest values of metals removal were achieved for autolysed mycelia while the lowest levels were observed in the presence of glucose.     

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.     

改性γ-聚谷氨酸络合重金属离子性能

研究了不同控制条件(温度、Pb2+浓度、pH)对交联改性γ-聚合谷氨酸(γ-PGA)吸附重金属离子所形成的絮凝颗粒性质的影响,对于治理水中重金属污染的相关研究有一定参考价值。实验表明,C-L-γ-PGA絮凝吸附Pb2+的最佳温度段在30℃附近。随着交联度的增加,不同的Pb2+浓度影响絮凝颗粒的大小,当处于较低浓度时,静电引力成为影响絮凝颗粒粒径最主要的因素,当Pb2+浓度增加到一定程度时,重金属的吸附量成为絮凝颗粒的粒径的决定因素。溶液pH达到7附近时,能够形成粒径最大的絮凝颗粒,并出现了最大的Pb2+去除率。C-L-γ-PGA对其他重金属离子也有类似的吸附絮凝作用,且絮凝吸附强弱顺序为Cu2+>Cr3+>Pb2+>Hg2+。吸附絮凝颗粒的粒径反映了重金属被吸附之后分离的难易程度,因此研究不同条件对絮凝颗粒粒径的影响对重金属离子的吸附和去除有重要意义。     

Sequestering of heavy metal ions from aqueous solutions by using a lignocellulosic material

The ability of Brown Stock Washer (BSW) unbleached kraft pulp and Chemi-Thermo-Mechanical Pulp (CTMP) to sequester heavy metals was studied. The BSW pulp is chemically produced while the CTM one is produced by mechanical treatment aided by some chemicals. The two pulps were rendered in their protonated form and then equilibrated with two aqueous solutions of metals. One was ocean water and the other was a laboratory prepared solution of metal ions. Both pulps were able to remove metal ions from the solution in a one-stage procedure. The overall metal removal efficiency of CTMP was in general greater than that of the BSW pulp for the low concentration metals.     

Estimation of atmospheric trace metal emissions in Vilnius City, Lithuania, using vertical concentration gradient and road tunnel measurement data

A new approach for the estimation of trace metal emissions in Vilnius city was implemented, using vertical concentration profiles in the urban boundary layer and road tunnel measurement data. Heavy metal concentrations were examined in fine and coarse particle fractions using a virtual impactor (cut-off size diameter 2.5 μm). Negative vertical concentration gradients were obtained for all metals (Ba, Pb, V, Sb, Zn) and both fractions. It was estimated that the vertical concentration gradient was formed due to emissions from an area of about 12 km². Road tunnel measurements indicated that trace metal concentrations on fine particles were lower than those on coarse particles, which suggested that re-emitted road dust was highly enriched in trace metal due to historic emissions within the tunnel. Emission rates of different pollutants in the road tunnel were calculated using pollutant concentration differences at the tunnel entrance and exit and traffic flow data. Heavy metal emission rates from the area of Vilnius city were estimated using the vertical gradient of heavy metal concentrations and the coefficient of turbulent mixing, as derived from meteorological measurement data. The emission values calculated by the two different methods coincided reasonably well, which indicated that the main source of airborne trace metals in Vilnius city is traffic. The potential of the vertical concentration gradient method for the direct estimation of urban heavy metal emissions was demonstrated.     

Enhanced removal of heavy metals in primary treatment using coagulation and flocculation.

The goal of this study was to determine the removal efficiencies of chromium, copper, lead, nickel, and zinc from raw wastewater by chemically enhanced primary treatment (CEPT) and to attain a total suspended solids removal goal of 80%. Operating parameters and chemical doses were optimized by bench-scale tests. Locally obtained raw wastewater samples were spiked with heavy metal solutions to obtain representative concentrations of metals in wastewater. Jar tests were conducted to compare the metals removal efficiencies of the chemical treatment options using ferric chloride, alum, and anionic polymer. The results obtained were compared with those from other studies. It was concluded that CEPT using ferric chloride and anionic polymer is more effective than CEPT using alum for metals removal. The CEPT dosing of 40 mg/L ferric chloride and 0.5 mg/L polymer enhanced heavy metals removal efficiencies by over 200% for chromium, copper, zinc, and nickel and 475% for lead, compared with traditional primary treatment. Efficient metals capture during CEPT can result in increased allowable headworks loadings or lower metal levels in the outfall.     

Removal of heavy metal ions from water by complexation-assisted ultrafiltration

Toxic heavy metals in air, soil and water are global problems that are growing threat to the environment. Therefore, the removal and separation of toxic and environmentally relevant heavy metal ions are a technological challenge with respect to industrial and environmental application. A promising process for the removal of heavy metal ions from aqueous solutions involves bonding the metals to a bonding agent (such as macromolecular species), and then separating the loaded agents from wastewater by separation processes such as membrane filtration. The choice of water-soluble macroligands remains important for developing this technology. The effects of type of complexing agent, pH value and applied pressure on retention coefficients of Zn(II) and Cd(II) complexes were investigated. At best operating conditions (pH=9.0, p=300kPa) using diethylaminoethyl cellulose, the removal of Cd(2+) and Zn(2+) was more than 95% and 99%, respectively.     

Macrophyte growth in a pilot-scale constructed wetland for industrial wastewater treatment

A pilot-scale wetland was constructed to assess the feasibility of treating the wastewater from a tool industry in Santo Tomé, Santa Fe, Argentina. The wastewater had high conductivity and pH, and contained Cr, Ni and Zn. This paper describes the growth of vegetation in the experimental wetland and the nutrient and metal removal. The wetland was 6 x 3 x 0.4 m. Water discharge was 1000 l d(-1) and residence time was 7d. After the wetland was rendered impermeable, macrophytes from Middle Paraná River floodplain were transplanted. Influent and effluent quality was analyzed every 15 d. TP, Cr, Ni and Zn concentrations in leaves, roots and sediment (inlet and outlet) were measured monthly. Cover and biomass of predominant species were estimated. Also, greenhouse experiments were carried out to measure the effects of conductivity and pH on floating species. The variables measured in the influent were significantly higher than those in the effluent, except for HCO(3)(-) and NH(4)(+). TP and metal concentrations in sediment at the inlet were significantly higher than those at the outlet. Conductivity and pH of the incoming wastewater were toxic for the floating species. Typha domingensis displaced the other species and reached positive relative cover rate and biomass greater than those at the undisturbed natural environment. T. domingensis proved to be highly efficient for the treatment of wastewater. For that reason, it is the advisable species for the treatment of wastewater of high conductivity and pH enriched with metals, characteristic of many industrial processes.     

Heavy metals removal in fixed-bed column by the macro fungus Pycnoporus sanguineus

The ability of Pycnoporus sanguineus to adsorb heavy metals from aqueous solution was investigated in fixed-bed column studies. The experiments were conducted to study the effect of important design parameters such as column bed height, flow rate and initial concentration of solution. The breakthrough profiles were obtained in these studies. A mathematical model based on external mass transfer and pore diffusion was used for the prediction of mass transfer coefficient and effective diffusivity of metals in macro-fungi bed. Experimental breakthrough profiles were compared with the simulated breakthrough profiles obtained from the mathematical model. Bed Depth Service Time (BDST) model was used to analyse the experimental data and evaluated the performance of biosorption column. The BDST model parameters needed for the design of biosorption columns were evaluated for lead, copper and cadmium removal in the column. The columns were regenerated by eluting the metal ions using 0.1 M hydrochloric acid solution after the adsorption studies. The columns were subjected to repeated cycles of adsorption of same metal ions and desorption to evaluate the removal efficiency after adsorption-desorption.     

Metabolic fate of [14C]-2,4-dichlorophenol in macrophytes

The metabolic fate of 2,4-dichlorophenol (DCP) was investigated in six macrophytes representing different life forms. Salvinia natans and Lemna minor were chosen as surface-floating plants, Glyceria maxima and Mentha aquatica as emergent species and Myriophyllum spicatum and Hippuris vulgaris as submerged aquatic plants. After uptake of a [U-phenyl-14C]-DCP solution followed by a 48 h water chase, whole plants (L. minor, S. natans) or excised shoots were harvested and aqueous extracts were analysed by high performance liquid chromatography (HPLC). Metabolites were then isolated, submitted to enzymatic or chemical hydrolyses and characterised by electrospray ionisation-mass spectrometric analyses. Whereas DCP monoglucosides or more complex monoglucoside esters, either malonyl or acetyl, were found in most species, an unusual glucosyl-pentose conjugate was identified as the DCP major metabolite in L. minor and G. maxima. Our results showed for the first time the ability of five macrophytes to uptake and metabolise DCP and the characterisation of their metabolic pathways of DCP biotransformation.     

Effects of macrophytes and external carbon sources on nitrate removal from groundwater in constructed wetlands

Several microcosm wetlands unplanted and planted with five macrophytes (Phragmites australis, Commelina communis, Penniserum purpureum, Ipomoea aquatica, and Pistia stratiotes) were employed to remove nitrate from groundwater at a concentration of 21-47 mg NO3-N/l. In the absence of external carbon, nitrate removal rates ranged from 0.63 to 1.26 g NO3-N/m2/day for planted wetlands. Planted wetlands exhibited significantly greater nitrate removal than unplanted wetlands (P<0.01), indicating that macrophytes are essential to efficient nitrate removal. Additionally, a wetland planted with Penniserum showed consistently higher nitrate removal than those planted with the other four macrophytes, suggesting that macrophytes present species-specific nitrate removal efficiency possibly depending on their ability to produce carbon for denitrification. Although adding external carbon to the influent improved nitrate removal, a significant fraction of the added carbon was lost via microbial oxidation in the wetlands. Planting a wetland with macrophytes with high productivity may be an economic way for removing nitrate from groundwater. According to the harvest result, 4-11% of nitrogen removed by the planted wetland was due to vegetation uptake, and 89-96% was due to denitrification.