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Review

Biosorption of Heavy Metals with Algae: Critical Review of Its Application in Real Effluents

1
Departamento de Ingeniería Química y Procesos de Minerales, Universidad de Antofagasta, Antofagasta 1240000, Chile
2
Departamento de Biotecnología, Universidad de Antofagasta, Antofagasta 1240000, Chile
*
Author to whom correspondence should be addressed.
Sustainability 2023, 15(6), 5521; https://doi.org/10.3390/su15065521
Submission received: 17 February 2023 / Revised: 13 March 2023 / Accepted: 16 March 2023 / Published: 21 March 2023
(This article belongs to the Special Issue Environmental Water, Air, and Soil Pollution)

Abstract

:
Biosorption is a variant of sorption techniques in which the adsorbent is a material of biological origin. It has become an economic and ecological alternative for the treatment of effluents. Among the biomasses employed in biosorption, algae have emerged as a sustainable solution for producing environmentally friendly adsorbents due to their abundance in seawater and freshwater, profitability, reuse and high metal absorption capacities. Although the research on the use of biosorbents is extensive and has grown in recent years, there are not many cases of their use for the treatment of real industrial solutions, which are more challenging due to the complex composition of metals that results in interference or competition over the functional sites of the biomass. This review aims to highlight the current state of research, focusing on the application of algae biosorption to remove copper from effluents. The most studied metals are those with the most significant health connotations, such as Cd, Cu and Pb. Regarding copper, only 2% of the biosorption works using seaweeds have been applied to real effluents, which leaves a relevant gap to advance the technology in the treatment of polluted solutions.

Graphical Abstract

1. Treatment Techniques for Heavy Metals Contaminated Effluents

Nowadays, heavy metal pollution is one of the most critical environmental problems. Many activities produce and discharge wastes containing heavy metals into the environment, such as mining, tanneries, smelters, energy and fuel producers, chemical and electroplating industries, etc. Thus, metal pollution harms human health and the ecosystem [1].
Reliable methods to decontaminate heavy metals from aquatic sources and wastewater are necessary. Numerous treatment methods have been designed to remove heavy metals effectively; precipitation, reverse osmosis, ion exchange, ultrafiltration, nanofiltration, coagulation, flocculation, flotation, electrodialysis and adsorption are examples of technologies vastly applied by industries. Nevertheless, these techniques have disadvantages associated with the selectivity, costs and generation of secondary wastes. Adsorption is an economical and practical process that has become one of the most preferred treatments for heavy metal removal [2]. The extensive use of activated carbon, an efficient adsorbent, is restricted by its high price and limited reusability [3]. In that perspective, biosorption, i.e., using biomaterials as adsorbents, has surfaced as a promising method with high efficiency even at minute amounts of adsorbent, due to low costs, no additional nutrient requirements, easy handling and zero detrimental effects on the environment [4].
The biosorption process effectively allows certain types of biomass to sequester organic or inorganic contaminants [5] capable of binding and concentrating selective ions present in aqueous solutions, thanks mainly to an affinity between the adsorbate and the biosorbent. The practice of biosorption technology has the advantages of low operating cost, environmental friendliness, better performance, biosorbent reuse, short operation time, high specificity and absence of formation of secondary contaminants [6]. Bacteria, algae, fungi, animal and fruit skin, plant residues, activated sludge and biopolymers are different biosorbents. Diverse types of seaweed have been the subject of intensive research, which evaluates metal sorption performance and efficiencies in various wastewater environments [7].
In the case of the mining industry, generation of mineral wastes is inherent in the exploitation of ores and metal beneficiation methods [8]; the amount of waste generated by mining makes this industry one of the most intensive in the consumption of raw materials and the use of land to dispose of its waste [9]. The primary mining wastes are overburden, low-grade ores, tailings and slags produced in different stages of mining and mineral processing [10,11].
Among the impacts produced by mining beyond the eventual generation of acid drainage is the dispersion of heavy metals to the soils surrounding mineral waste deposits, which is a critical aspect in cases where tailings and wastewater treatment facilities are located (Figure 1). Thus, the polluting effect of potentially toxic elements on soils has been reported in mining regions such as Morocco, Iran, China, Australia and Chile [12,13,14,15]. One case study reports on this in the city of Taltal, Chile, which has a long mining history. Gold-copper tailings were dumped on the beach without environmental protection for many years and inserted into the urban radius. These abandoned tailings have recently been shown to have substantially elevated geochemical levels of heavy metals in the surrounding soils of the city. Cd, Cu, Zn, Cr and Pb concentrations exceed those recommended in evaluations of ecological risk and human health [12].
As mentioned, mining activities may severely impact the environment by releasing heavy metals and other species into soils and watercourses that destroy vegetation, crops and ecological equilibrium. In addition, the polluting effect and accumulation of metals in the human body have been widely reported, including anemia, respiratory, gastrointestinal and nervous diseases and cancer [20,21,22]. The mining industry, like other activities, has widely adopted conventional active chemical treatments to mitigate contamination events, mainly by neutralization. This technique involves adding alkaline reagents such as limestone, calcium oxide, caustic soda and sodium carbonate, among others, to increase the pH and precipitate dissolved heavy metals [23,24]. Other methods, such as ion exchange and activated carbon adsorption, solvent extraction and chemical precipitation, have been used by similar industries. However, high amounts of energy and chemical agents required and the generation of large quantities of secondary waste are drawbacks that limit their broad application. In addition, the efficiency for very dilute solutions is generally low [25].
Other techniques based on a biological approach have been gradually applied to treat mining tailings and other industrial wastewater due to their biodegradability and cost-effectiveness at low heavy metals concentrations [26]. Some examples of these bioremediation techniques correspond to phytostabilization, where plants stabilize metallic contaminants in mine effluents, and bioimmobilization, where microorganisms promote the biogenesis of insoluble species like jarosite [27,28]. In a novel approach, the biorecovery of metals from industrial wastewater, i.e., obtaining critical metals or metal nanoparticles through bacteria and other biomasses, is an emerging field of study [29,30,31].
The mechanisms governing the different bioremediation procedures include bio-weathering, microbial reduction, biomineralization, bioaccumulation and biosorption [32]. Biosorption can be classified using different criteria, such as the metabolism dependence of metal-biosorbent interaction and the location where that interaction occurs [25].
In recent decades, research on biosorption has been increasing; scientific articles maintain an upward trend in terms of knowledge development. However, the application in real conditions of bioadsorption to treat real discharges from industrial operations is still incipient. The move to a new level requires further research on the handling of complex solutions composed of various metals and in conditions of greater instability for biomasses. In this article, together with a review of the background of biosorption as a subject of study, a compilation of cases applying the removal of copper from real effluents is made.

2. Biosorption Process

The first works on biosorption were published in the mid-20th century. Since then, significant efforts have been made to describe and prepare effective and inexpensive biomaterials for biosorption, mainly for wastewater treatment. The use of various biomasses as sorbents has demonstrated the ability to selectively remove toxic contaminants from aqueous solutions at low levels and under a wide spectrum of conditions, which has given it attention from various fields. Progress has been achieved in understanding the complex mechanisms involved in biosorption by defining the quantification methods (equilibrium and kinetics) and determining the influencing factors that affect efficiency and rate [33].
Adsorption is the physicochemical adhesion of ions and molecules onto the surface of a solid material [34]. Physical metal-biosorbent interaction involves electrostatic and Van der Waals forces, while the chemical basis is related with ion exchange, proton shift, complexation and metal chelation [35,36]. Biosorption is a rapid and reversible process where ions from aqueous solutions bind to functional groups present on the surface of biomasses, independent of cellular metabolism [37].
Biosorption is a clean and straightforward alternative for recovering metals in diluted solutions that require low capital investment costs. It employs renewable, inexpensive sorbents, which can be obtained from cultures and secondary sources such as bacteria, algae, fungi, agro-industrial and aquaculture wastes [37,38]. The influencing factors on biosorption depending on metal characteristics are concentration, molecular weight, ionic radius and oxidation state. On the other side, the properties that are affected by biosorbent features and operational conditions are biosorbent concentration, pH and temperature. Among all the influencing factors, pH is one of the most important because it controls the ionic dissociation and speciation of sites and metals in the solution [39]. Table 1 presents the properties of the biosorption process in terms of cost, biosorbent storage, metal selectivity and biosorbent reusability.
Among the beneficial aspects of biosorption when using stabilized (dead) biomass is the ability to store biosorbents for long periods. There is no toxicity effect due to the presence of heavy metals or limitation by nutrients, a wide range of pH and temperature work and the possibility of chemical regeneration for reuse in adsorption–desorption cycles [40,42,43].
The main studies on biosorbents have been led by microorganisms (bacteria and cyanobacteria), fungi and macroalgae (and their extracts). There are other biomasses, such as plants, that also contribute to the knowledge about biosorption to a lesser extent. All the biomasses have in common the presence of a cell wall formed by biopolymers; these chains are composed differently in each organism type, e.g., cell walls of bacteria are composed of peptidoglycan, algal by fucoidan and alginate and fungi by chitin (Figure 2). Each biopolymer has chemical residues that offer chemical groups that interact with metals leading to its physical retention or chemical complexation that results in biosorption.
Metal biosorption has been extensively approached from a mechanistic perspective and, on the basis of demonstrating the capacity of the biomass, to be able to carry out the removal/recovery of various metals. For this purpose, the literature strongly shows the use of monometallic solutions of defined concentrations or in mixtures with established proportions. These experiments have made it possible to elucidate many of the phenomena that occur during biosorption and operating conditions that are best for biosorption and that are specific to the metalbiosorbent interaction [25].
Biosorption is the subject of increasing research attention. Within the last 30 years, the biosorption applied to the recovery of heavy metals has had a notable development, although it was only in the last few years that the demand for studying different biomasses has had an increase in publications. By 2021, the maximum number of biosorption studies were reported. Heavy metals biosorption using bacteria has been the most studied (Figure 3).

3. Marine Algae as Biosorbents

When choosing the biomass for metal biosorption, its origin is a major factor to be considered. Several bacterial, fungal and yeast biomasses were found to possess excellent biosorption capacity due to their cell wall composition; however, most of these biomasses need to be cultured [1,44]. The culturing increases the costs and poses more demands for maintaining a continuous supply of biomass [45].
Of the many biosorbents recently investigated, i.e., fungi, bacteria and algae, brown algae biomass has been shown to be highly effective in terms of its ability to sequester heavy metals reliably and predictably [46].
Seaweeds are plentiful and very fast-growing biological resources available in many parts of the world. In some oceans, they threaten the tourist industry by spoiling pristine environments and fouling beaches; thus, utilizing seaweeds as biosorbents can be beneficial to local economies [47]. Seaweeds are an excellent biosorbent for different metal ions, and the advantages seem to outweigh the limitations (Table 2) [48,49].
Marine algae are classified into three main sub-groups according to the evolutionary pathways that are reflected by their dominant pigmentation: brown (Phaeophyta), red (Rhodophyta) and green (Chlorophyta). In addition, the cell walls are composed of different substances, which can be related to biosorption performances [50,51]. The cell walls of brown algae generally contain three components: cellulose, alginic and guluronic acids, which are predominantly composed of carboxyl and sulfated groups. Red algae also contain cellulose and sulfated polysaccharides such as agar and carragenates. Green algae walls are mainly composed of cellulose, and a high percentage are proteins bonded to polysaccharides forming glycoproteins [50,52].
Among biosorbents, macroalgae are a promising group for metal biosorption because the complex mucilaginous polysaccharides composing cell walls have a high affinity for di- and trivalent cations (Figure 2) [53,54,55]. Although the use of seaweeds has been validated for wastewater treatment, it has been preferably done for diluted or pure solutions [50,56].
From the published literature, among the three groups of algae (red, green, brown algae) brown has received the most attention. Higher uptake capacity has been found more for brown algae than red and green algae [57], which may result from the predominant functional groups composing cell walls [49]. The lowest biosorption uptake corresponds to green algae, which are poor in fucoid substances. The presence of alginates in the cell walls of brown algae, as well as carrageenan in those of red algae, is responsible for the binding of metals to biomass. Alginate has a high affinity for bivalent metals, which is reflected by the maximum biosorption uptake, qmax, where brown algae have higher uptake than other types of algae [11].
The removal performance of many metals for brown algae has been extensively studied, including lead, copper, cadmium, zinc, nickel, chromium, uranium and gold. The qmax for all the studied heavy metals and species of brown algae are quite high, between 0.39 and 1.66 mmol/g [58,59]. In general, for a same alga, the uptake follows the preference order Pb > Cu ≈ Ni > Cd > Zn. The genus Sargassum sp. seems to be the best for the uptake of metals among brown algae. In recent years, more studies have reported on the performance of green and red algae for the biosorption of heavy metals. The heavy metals in these studies include lead, copper, cadmium, zinc and chromium. Although both types of algae can remove heavy metal ions from aqueous solutions, the performance is far below that of brown algae [51].

4. Heavy Metals Biosorption by Algae

In the context of biosorption, seaweed is mostly used in the wastewater treatment for reducing or removing toxic heavy metal contents [51]. The removal of heavy metals from aquatic courses constitutes a relevant environmental challenge today due to the toxic nature of these elements for living organisms [60]. Some heavy metals are toxic and carcinogenic, even in tiny concentrations, and they are non-biodegradable and can easily accumulate in living organisms. The heavy metal accumulation in soils and groundwaters is a growing concern; the main anthropogenic sources are mining operations, smelters, the paint industry, fertilizers, leather tanning, electroplating, alloy and battery manufacturing [7].
When evaluating the most studied metals for biosorption with algae, cadmium has the highest number of publications, with approximately 23% of reports based on how toxic it is in the environment and its critical removal. Likewise, it is an indicator that biotechnological methods represent a competitive alternative to traditional processes. Subsequently, copper and lead (20% and 19%, respectively) are found, which are heavy metals highly diffused by mining and industrial operations. The biosorption of more abundant metals, such as iron (3%), has been less studied because the methods of precipitation by neutralizing agents are quite effective and cheap, which does not support a sustained motivation for their investigation (Figure 4).
Research on algal biosorption is concentrated on brown algae due to the aforementioned metal-affinity properties. However, the review of articles studying green and red algae to capture metals is increasingly recurrent (Table 3).

4.1. Brown Seaweeds

Chromium, nickel, copper, arsenic, cadmium, mercury and lead are globally alarming heavy metals [73]. Pb and Cr are some of the most frequent toxic cations in wastewater. Ali et al. [61] studied two brown seaweed species Hydroclathrus clathratus and Cystoseira barbata for Pb and Cr biosorption, concluding that metal concentration had an inverse effect on the metal uptake. Maximum biosorption efficiency was achieved at 120 min, pH 5 and 10 g/L of algae. The maximum uptakes of Pb and Cr biosorption are 4.97, 7.19 mg/g on H. clathratus and 4.61, 7.30 mg/g on C. barbata, respectively.
Plaza Cazón et al. [62] used Macrocystis pyrifera to remove zinc and cadmium from mono- and bimetallic solutions, demonstrating in both cases goods uptake capacities, which were similar to other studies performed with Sargassum filipendula, Gymnogongrus torulosus and Fucus vesiculosus, other species reported in previous works [58,64]. In addition, M. pyrifera and Undaria pinnatifida removed chromium and mercury from aqueous solutions. It was demonstrated that the carboxylic and amino groups are strongly involved in chromium binding, while amino and sulfhydryl are for mercury uptake, establishing that the interaction would be specific between metal and functional groups [62,63].
Brown alga Sargassum sp. was used to remove Pb and Cu from stormwater, resulting in biosorption capacities of 196.1 mg/g and 84.0 mg/g for Pb and Cu, respectively. The analysis of the functional groups of the algae using FTIR showed that the carboxyl was mainly responsible for biosorption [65].
The use of alginate from seaweed has also been validated. Barquilha et al. [74] used alginate from Sargassum sp. as a biosorbent for Ni and Cu ions from synthetic solutions and actual electroplating effluents. The experiments were carried out at pH 4.5. The maximum sorption capacity (qmax) of up to 1.147 mmol/g for Ni ions and 1.640 mmol/g for Cu ions. The biosorption of Ni and Cu from actual electroplating effluents with high concentrations of light metals becomes highly competitive, decreasing the amount of biosorbed Ni and Cu ions due to the effect of ionic strength.
On the other hand, a metal that shows considerable interest in its recovery is copper; despite being an essential element, when its concentration is high, it is potentially toxic. This generates the need to develop procedures for its elimination from natural environments. In that context, biosorption has been proven to be a very useful tool for its removal [41]. An advantage of the biosorption of copper with algal biomasses is the possibility of using dead biomass that handles mining effluents, which have unfavorable chemical characteristics for cell growth (acidity, ionic strength, and heavy metal content). Several algae can be cultivated in sea farms and are therefore considered a reliable source of supply. On the other hand, the biomass acts as an ion exchanger; therefore, the process is carried out quickly, and desorption of the metal is relatively easy. The use of marine algae, predominantly brown algae, to remove heavy metals from solutions through the mechanisms of biosorption and bioaccumulation was reviewed by Yadav et al. [75].
Lessonia nigrescens biomass was used to biosorb Cu in solution at pH 5 and contact time 120 min where the best data fit was the Langmuir isotherm model, obtaining a maximum biosorption capacity of 60.4 mg/g. The dead biomass of the brown algae L. nigrescens captures Cu ions in solution by surface interactions with different functional groups, such as carboxyl, hydroxyl, sulfonate and amide groups, but not amine groups [66].

4.2. Red Seaweeds

Cadmium was recovered from aqueous solutions with red alga Ceramium virgatum where experimental parameters that affect the biosorption process, such as pH, contact time, biomass dosage and temperature were studied. The C. virgatum monolayer biosorption capacity for Cd(II) was 39.7 mg/g ions [69]. Chaisuksan [67] studied the bioadsorption of pretreated red algae Gracilaria fisheri for cadmium and copper. The maximum uptake values were 0.63 and 0.72 mmol/g, respectively. Bioadsorption capacity increased as pH increased up to a plateau of four. Absorption rates for cadmium and copper were rapid with 90% biosorption completed in 30 min.
On the other hand, studies have removed Cu(II), Co(II) and Zn(II) ions from aqueous media using alginate extracted from the biomass of marine red algae Callithamnion corymbosum. The maximum biosorption capacities follow the order: Cu(II) (64.52 mg/g) > Zn(II) (37.04 mg/g) > Co(II) (18.79 mg/g), where the best biosorption conditions were at pH 4.4, biosorbent dose of 2.0 g/L and room temperature [70].

4.3. Green Seaweeds

The green algae Codium vermilara was used to remove copper, with an efficiency of about 85% under an algae dosage of 0.75 g/L, pH 5.3, contact time 70.5 min and copper concentration of 48.8 mg/L [71]. On the other hand, Chlorella vulgaris biosorbed copper with a recovery of 90.3% under pH 7, 105 min of contact time and 20 mg/L of initial copper concentration [72]. It was determined that the chemical groups involved in the green cell walls are preferably amine and carboxyl. The biosorption was extracellular due to the presence of copper on the cell surface.

5. New Challenges: Biosorption of Copper from Mining and Industrial Effluents Using Seaweeds

The search for cheap decontamination processes that do not generate secondary impacts is of growing interest. If to this is added the possibility that the remediation can recover valuable metallic species from effluents, it makes these processes more attractive for their implementation. Biosorption is a method that has been proven not only to remove contaminants but also to extract useful substances, e.g., recovery of precious metals and rare-earth elements with different biosorbents [76,77,78].
Although the advantages of biosorption have been widely demonstrated, the great challenge is to migrate from the lab scale to treat real effluents with less controlled parameters. In most studies, biosorption has been carried out using prepared solutions at known and generally pure metal concentrations in order to study the controlling variables. There are a few examples of algal biomasses being applied to real solutions where various metals are combined, and the pH and other conditions are not entirely fixed. Several cases are denoted in Figure 5.

5.1. Mining

Recently, the feasibility to biosorb copper from tailings of mining operations has been verified using the red algae Gracilaria chilensis [39]. It was determined that the copper biosorption occurred in 60 min and the maximum adsorption (0.31 mmol/g) was achieved with pH 1.5, 0.5 g/L of biomass dosage and 200 mg/L of initial Cu concentration, which is in the range of concentrations usually found for this metal in mining effluents. FTIR observations of G. chilensis demonstrated that the functional chemical groups carboxyl, hydroxyl and amines are involved in the biomass-metal interaction. These molecules are widely distributed in the basic biomolecules, such as proteins, carbohydrates and their derivative compounds, such as glycoproteins.

5.2. Chemical and Electroplating

Other industrial effluents that have been remediated for the elimination of copper through algae are those from paint, agrochemicals and electroplating operations, which together with mining are the main anthropogenic sources of copper in wastewater that may affect the environment and population health. Among them, there is no trend between a particular type of algae. Most of the publications referred to in this section have worked with moderate copper concentrations, between 10 and 100 mg/L, which shows that biosorption is more efficient in less concentrated solutions. Regarding the removal efficiencies, among the works that report this data, levels above 60% are obtained, which indicates that the expectations of use in the treatment of complex solutions are positive. The red algae Kappaphycus alvarezii reached 82% efficiency in 13 h [68].
Brown algae, which elicit the best experimental results in controlled laboratory situations, when used to remove copper from real effluents, achieve efficiencies between 60 and 75%, particularly the species Sargassum sp. and F. vesiculosus [79,80]. It should be considered that electroplating solutions frequently contain, along with copper, high levels of chromium, nickel and zinc, which are species that may interfere with metal-algae binding sites.

5.3. Sewage

The effluents produced in wastewater treatment plants are also a source of heavy metals. This is because the influxes are varied and many times not only the household contribution but also from small industries. The use of green microalgae has been evaluated for the removal of copper from this type of discharge.
In the work by Chan et al. [81], the microalgae Chlorella vulgaris and Spirulina sp. have achieved copper removals close to 82% for both species in isolation and as a mixture. Stabilized biomasses were used, confirming the metabolic independence of the biosorption process. More recently, other authors have used the cyanobacterium Phormidium sp., which was able to extract about 60% of the copper present in complex discharges from various sources in 18 d [82].
The growing literature associated with the biosorption of heavy metals, particularly copper, is evident. Many researchers dedicate efforts not only to elucidate the mechanisms involved in the metal-biomass interaction but also to determine the controlling variables and simulate and optimize the process. However, taking the research to more applied horizons, putting the algal biomass in contact with complex solutions of the industries is still incipient. This study found that only 2% of the publications on copper biosorption with algae used non-reconstituted effluents.

6. Concluding Remarks

Heavy metal biosorption is a technique that has been studied with increasing interest since the 1950s. Various authors recognize and frequently study the mechanisms by which the process is conducted and the variables that affect the process. The advantages that support this bibliographic forcefulness are the low cost of the raw materials that constitute biosorbents, especially algae, their availability and the ability to treat solutions where it is expensive to operate with other methods due to the low concentrations of metals.
Despite the above, some challenges must be overcome for biosorption to reach a level of development that establishes it as a recurring alternative in the remediation of industrial/mining effluents. The advancement of large-scale procedures and the application of biosorbents in real conditions are some examples of the barriers the scientific and technical community must address. Most biosorption studies using synthetic or bimetallic solutions do not consider the behavior of biosorbents with different competing sorbates or matrices whose physicochemical characteristics differ greatly from real conditions. Of course, when the focus is on understanding the phenomena and recognizing the metal-biosorbent response, these tests are adequate, but it is necessary to carry out the studies at new levels of applicability.
If it is desired to advance in the application of biosorption as a competitive effluent remediation strategy, it is necessary to increase the amount of applied research, which allows validation of the responses observed in the laboratory. The results observed in the publications are encouraging, considering the complexities of systems in which the number of participating ions and the properties of the medium do not facilitate the selectivity of the process. It is expected that in the future, as weaknesses are resolved, algae biosorption will find its place in industry and separation technologies.

Author Contributions

Conceptualization, J.I.O. and S.C.; formal analysis, J.I.O.; investigation, S.C., P.M. and I.S.; resources, J.I.O., S.C., P.M. and I.S.; writing—original draft preparation, J.I.O. and S.C.; writing—review and editing, J.I.O., S.C., P.M. and I.S.; supervision, J.I.O.; funding acquisition, J.I.O. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by ANID through the Anillo-grant ACT210027 and the National Ph.D. scholarship 21200227.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

The authors want to thank Universidad de Antofagasta and the PhD in mineral process engineering program for their infrastructure support.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Mining and industrial wastewater discharges. (A) Mining effluent treatment facility for heavy metal removal [16], (B) addition of neutralizer for stabilization of acid mine drainage in a mining effluent [17], (C) discharge of wastewater in ponds [18] and (D) tailings deposit [19].
Figure 1. Mining and industrial wastewater discharges. (A) Mining effluent treatment facility for heavy metal removal [16], (B) addition of neutralizer for stabilization of acid mine drainage in a mining effluent [17], (C) discharge of wastewater in ponds [18] and (D) tailings deposit [19].
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Figure 2. The general structure of cell walls of the most used biosorbents and main polysaccharides involved in metal biosorption.
Figure 2. The general structure of cell walls of the most used biosorbents and main polysaccharides involved in metal biosorption.
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Figure 3. Bibliometric analysis associated with the publications reported in the WOS database on biosorption of heavy metals by the most used biomasses between 1990 and 2022. A publication could account for more than one type of biomass, so the number of articles should be taken as a reference and not as an exact account for each category.
Figure 3. Bibliometric analysis associated with the publications reported in the WOS database on biosorption of heavy metals by the most used biomasses between 1990 and 2022. A publication could account for more than one type of biomass, so the number of articles should be taken as a reference and not as an exact account for each category.
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Figure 4. Profile of investigations reported in the WOS database on biosorption of different heavy metals with alga biomasses. A publication can address more than one metal, so the number of articles should be taken as a reference and not as an exact account of each category.
Figure 4. Profile of investigations reported in the WOS database on biosorption of different heavy metals with alga biomasses. A publication can address more than one metal, so the number of articles should be taken as a reference and not as an exact account of each category.
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Figure 5. Research on applied biosorption of copper by algae as biosorbents. Applied biosorption considers the treatment of actual effluents.
Figure 5. Research on applied biosorption of copper by algae as biosorbents. Applied biosorption considers the treatment of actual effluents.
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Table 1. Properties of the biosorption process.
Table 1. Properties of the biosorption process.
PropertySpecificationRefs.
CostLow. Most sorbents are made from waste or renewable materials.[4,5,40]
StorageEasy. Dried materials can be stabilized for years.[41]
SelectivityMedium. The selectivity can be chemically improved by modifying biosorbent surfaces.[7,32]
Sorbent recovery and reusabilityHigh. Biosorbents are frequently reused for many cycles.[4,5,7]
Table 2. Advantages and disadvantages of using algal biomass for heavy metals removal from wastewater.
Table 2. Advantages and disadvantages of using algal biomass for heavy metals removal from wastewater.
AdvantagesDisadvantages
Biomass is renewable and low cost of obtainingIf dead biomass is used, energy is needed for drying
Biomass can be used dead (no nutrients or oxygen required)Microalgae have limited applicability in batch systems
Biomass can be regenerated (reusability)Microalgae biomasses need to be immobilized
Selective for many heavy metals
High uptake capacity
Immobilization is not mandatory (macroalgae biomasses)
No generation of residual sludge
Few chemicals needed for desorption and regeneration
Table 3. Seaweeds studied in biosorption and the metals considered.
Table 3. Seaweeds studied in biosorption and the metals considered.
TypeSpeciesMetalRefs.
BrownHydroclathrus clathratusPb, Cr[61]
Cystoseira barbataPb, Cr[61]
Macrocystis pyriferaZn, Cd, Ni[62,63]
Fucus vesiculosusCd, Pb, Cu[58]
Sargassum filipendulaCd, Zn[64]
Undaria pinnatifidaHg[63]
Sargassum sp.Pb, Cu[65]
Lessonia nigrescensCu[66]
RedGracilaria chilensisCu[39]
Gracilaria fisheriCd, Cu[67]
Kappaphycus alvareziiCr, Ni, Cu[68]
Ceramium virgatumCd[69]
Callithamnion corymbosumCu, Co, Zn[70]
GreenCodium vermilaraCu[71]
Chlorella vulgarisCu[72]
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Ordóñez, J.I.; Cortés, S.; Maluenda, P.; Soto, I. Biosorption of Heavy Metals with Algae: Critical Review of Its Application in Real Effluents. Sustainability 2023, 15, 5521. https://doi.org/10.3390/su15065521

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Ordóñez JI, Cortés S, Maluenda P, Soto I. Biosorption of Heavy Metals with Algae: Critical Review of Its Application in Real Effluents. Sustainability. 2023; 15(6):5521. https://doi.org/10.3390/su15065521

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Ordóñez, Javier I., Sonia Cortés, Pablo Maluenda, and Ignacio Soto. 2023. "Biosorption of Heavy Metals with Algae: Critical Review of Its Application in Real Effluents" Sustainability 15, no. 6: 5521. https://doi.org/10.3390/su15065521

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