Abstract
Heavy metal pollution is a major problems in the environment. The impact of toxic metal ions can be minimized by different technologies, viz., chemical precipitation, membrane filtration, oxidation, reverse osmosis, flotation and adsorption. But among them, adsorption was found to be very efficient and common due to the low concentration of metal uptake and economically feasible properties. Cellulosic materials are of low cost and widely used, and very promising for the future. These are available in abundant quantity, are cheap and have low or little economic value. Different forms of cellulosic materials are used as adsorbents such as fibers, leaves, roots, shells, barks, husks, stems and seed as well as other parts also. Natural and modified types of cellulosic materials are used in different metal detoxifications in water and wastewater. In this review paper, the most common and recent materials are reviewed as cellulosic low-cost adsorbents. The elemental properties of cellulosic materials are also discussed along with their cellulose, hemicelluloses and lignin contents.
Similar content being viewed by others
Introduction
Heavy metals are elements which have atomic density more than 5. Some toxic heavy metals, such as lead, cadmium, nickel, cobalt, chromium, arsenic, iron and zinc, cause metal toxicity in living organisms . The major metal polluting industries are tannery, electroplating, textile, fertilizer, pesticide and metal processing industries as well as mining sectors. These toxic metals are major pollutants of freshwater reserves (Babarinde et al. 2006). Most of the metals are non-biodegradable, highly toxic and carcinogenic in nature. Toxic heavy metals reach through various food chains and cause toxic effects on the ecosystem as well as humans and animals. Therefore, it is necessary to treat metal-contaminated wastewater before its discharge into the environment.
A number of technologies are available to treat heavy metal-laden wastewater. Among them, some popular techniques are chemical precipitation (Ku and Jung 2001), ion exchange (Alyüz and Veli 2009), adsorption (Park et al. 2007; Kongsuwan et al. 2009; Guo et al. 2010), ultrafiltration (Landaburu-Aguirre et al. 2009; Sampera et al. 2009), reverse osmosis (Shahalam et al. 2002; Mohsen-Nia et al. 2007), nanofiltration (Murthy and Chaudhari 2008; Muthukrishnan and Guha 2008; Nguyen et al. 2009; Figoli et al. 2010), electrodialysis (Sadrzadeha et al. 2009; Nataraj et al. 2007), coagulation (El Samrani et al. 2008; Chang and Wang 2007), flocculation (Chang et al. 2009; Duan et al. 2010; Bratskaya et al. 2009), flotation (Lundh et al. 2000; Polat and Erdogan 2007) and electrochemical process (Heidmann and Calmano 2008; Nanseu-Njiki et al. 2009). Comparatively, the adsorption process seems to be a significant technique due to its wide applications, such as ease of operation, economical feasibility, wide availability and simplicity of design (Faust and Aly 1987).
For cellulosic low-cost biosorbents, agricultural waste or plant wastes are mostly used in heavy metal sequestration, due to their low economic value and widespread availability, and also the potential to treat wastewater at a large scale. The cellulosic plant materials used in heavy metal detoxification are rice husk (Sobhanardakani et al. 2013; Nakbanpote et al. 2000; Feng et al. 2006), wheat straw (Farooq et al. 2011, Dang et al. 2009; Dhir and Kumar 2010; Pehlivan et al. 2009a, b, c), banana peel (Memon et al. 2009; Sahu et al. 2013; Ajmal et al. 2000), grape bagasse (Farinella et al. 2007), corn stalk (Zheng et al. 2012), bel fruit shells (Anandkumar and Mandal 2009), coir pith (Parab et al. 2006), hemp fibers (Tofan et al. 2013) and corn cob (Buasri et al. 2012).
In the category of low-cost adsorbents, both non-cellulosic and cellulosic materials are used. In non-cellulosic materials, zeolites (Basaldella et al. 2007), clay (Adebowale et al. 2006), chitosan (Gamage and Shahidi 2007), red mud (Nadaroglu et al. 2010), dairy sludges (Sassi et al. 2010) and metal oxides (Mishra et al. 2004) are utilized as adsorbents. The use of cellulosic waste materials as adsorbent is considered as promising in the future. The main sources of cellulosic contents are agricultural waste material and industrial by-products. Non-agricultural wastes are also prominent, because these are also efficient in metal removal, as presented by many current studies.
In this review, cellulosic emerging modified or natural adsorbents has been characterized with the lignocellulosic and composite properties of widely used materials. The potential of cellulosic adsorbent materials for various heavy metal uptake capacities was also reported.
Techniques used in heavy metal removal
Many techniques are used at the present time for wastewater treatment. The present study will summarize the widely used technique for heavy metal removal from wastewater. For treatment of waste water, many methods are common, viz. precipitation, neutralization, membrane filtration, ion exchange, flotation and adsorption. Both, physical and chemical treatment technologies have been developed, such as the electrochemical process (Vlyssides and Israilides 1997), coagulation/flocculation (Song et al. 2006), oxidation (Szpyrkowicz et al. 2001), reverse osmosis (Hanra and Ramchandran 1996), membrane filtration (Sabry et al. 2007) and adsorption (Nagah and Hanafiah 2008) for treatment of different types of water. Among these, adsorption technology is the least expensive and effective separation technique for the removal of metal ions from industrial wastewater (Demirbas et al. 2008a, b).
Chemical precipitation
It is a simple and very common technique to remove heavy metals due to its ease in operation and inexpensive nature (Ku and Jung 2001). Chemical precipitation technique is used for the treatment of metal-containing wastewater by forming an insoluble precipitate through the addition of chemicals (Karthikeyan et al. 1996). Some other chemical precipitation techniques are also used such as hydroxide precipitation, sulfide precipitation and heavy metal chelating precipitation. As precipitant agents, lime and limestones are most commonly used in chemical precipitation due to being a simple process, convenience and effectiveness in treating inorganic effluents at higher concentrations (Mirbagherp and Hosseini 2004; Aziz et al. 2008). Despite the advantages, it also has some disadvantages, such as requiring an excess amount of chemicals in the treatment. It has some other drawbacks such as generation of excessive sludge and the problem of sludge disposal into the environment.
Ion exchange
The ion exchange method is basically based on the capability to exchange cations with metals in the wastewater (Maranon et al. 1999; Kononova et al. 2000; Monteagudo and Ortiz 2000; Pagano et al. 2000). There are different types of materials used, which may be natural (alumina, carbon, silicates) or synthetic (zeolites and resins). Among them, zeolites are most abundantly used in the ion exchange process (Fernandez et al. 2005). The ion exchange process takes place by both cations and anions exchange in aqueous medium by ion exchange. The drawback of this method is that it is highly sensitive to the pH of the solution, and the ion exchange is non-selective in operation.
Membrane process
The membrane filtration technique used different types of membranes and removal of various heavy metals in aqueous solution. This technique removes oils, suspended solids, heavy metals, and organic and inorganic materials (Barakat 2011; Fu and Wang 2011). Different forms of this technique are used based on the size of the particles, such as ultrafiltration (UF), nanofiltration (NF), reverse osmosis (OS) and electrodialysis (ED), depending on the type of wastewater.
Ultrafiltration
In this method, dissolved molecules, heavy metal ions and other contaminants are filtered using a membrane, according to their molecular size. Different types of membranes allow only the passage of low molecular solutes, and the remaining ones, such as larger molecules and heavy metals, do not pass through and are separated out. It has also been divided into subcategories, such as micellar enhanced ultrafiltration (Landaburu-Aguirre et al. 2012; Yurlova et al. 2002), complexation–ultrafiltration (Molinari et al. 2008) and chelating enhanced ultrafiltration (Kryvoruchko et al. 2002).
Nanofiltration
Nanofiltration is membrane separation technique that is used in heavy metal separation from aqueous solutions (Mohammad et al. 2004; Al-Rashdi et al. 2011). It is applied to the removal of different heavy metals such as copper (Cséfalvay et al. 2009; Ahmad and Ooi 2010), arsenic (Nguyen et al. 2009; Figoli et al. 2010), nickel (Murthy and Chaudhari 2008) and chromium (Muthukrishnan and Guha 2008). It is reliable, comparatively easy to operate and has low energy consumption than others (Erikson 1988).
Reverse osmosis
Reverse osmosis (RO) technique is used mainly for the separation and fractionation of organic and inorganic substances and heavy metals in aqueous and nonaqueous solutions. The RO technique can be used to treat different types of industrial effluents, viz., chemical, textile, petrochemical, electrochemical, food, paper and tannery industries (Mohsen-Nia et al. 2007). In combination with the pilot membrane reactor, this technique is efficient in metal removal at high level (Dialynas and Diamadopoulos 2009). It has some disadvantages also: it consumes high power for the pumping pressure and the restoration of the membrane.
Electrodialysis
Electrodialysis (ED) is a separation process in which dissolved ions are removed from one solution to another solution across a charged membrane under an electric field (Sadrzadeh et al. 2008; Mohammadi et al. 2005). It is used in the treatment of wastewater as well as in the production of drinking water from seawater, separation and recovery of heavy metals ions and in salt production (Sadrzadeha et al. 2009). It is applied for heavy metal removal, such as chromium (Nataraj et al. 2007), copper and ferrous (Cifuentes et al. 2009), by various researchers.
Flotation
Flotation has been widely applied for the removal of toxic metal ions from wastewater (Polat and Erdogan 2007; Waters 1990; Tassel et al. 1997; Tessele et al. 1998). Other techniques of flotation are ion flotation, dissolved air flotation (DAF) and precipitate flotation. DAF is a more commonly used process than any other flotation techniques in the removal of heavy metals from aqueous solutions (Zabel 1984).
Chemical coagulation
Coagulation technique is used to prepare colloids. Some coagulates are used, such as aluminum, ferrous sulfate and ferric chloride that neutralize impurities present in wastewater/water. It is an important method showed by various researchers (El Samrani et al. 2008; Chang and Wang 2007). Ferric chloride solution and polyaluminium chloride (PAC) coagulants are used in heavy metal removal (El Samrani et al. 2008).
Electrochemical method
Electrochemical methods involves the redox reactions for metal removal under the influence of external direct current in the electrolyte solution. The coagulation process destabilizes colloidal particles by adding a coagulant and results in the sedimentation process (Shammas 2004). For increase in the rate of coagulation, the flocculation process takes place which enhances the change of unstable particles into bulky floccules (Semerjian and Ayoub 2003).
Adsorption
Adsorption is a very significantly economic, convenient and easy operation technique. It shows high metal removal efficiency and is applied as a quick method for all types of wastewater treatments. It is becoming a popular technique, because in this process the adsorbent can be reused and metal recovery is possible (Barakat 2011; Fu and Wang 2011; Zamboulis et al. 2011).
Activated carbon (AC)
At present, activated carbon (AC) is the mostly used adsorbent worldwide. AC is not only efficient in removal of heavy metals, but also for other contaminants present in water/wastewater. These can be used in both batch and column mode operation due to its high surface area, microporous structure and porosity properties. In the preparation of activated carbon, many agricultural waste biomasses are used such as bagasse (Onal et al. 2007), coconut shell, tea waste, peanut hull (Oliveira et al. 2009), apple waste (Maranon and Sastre 1991), sawdust (Ajmal et al. 1998), rice husk (Naiya et al. 2009), banana pith (Low et al. 1995), tree bark (Gundogdu et al. 2009) and activated cotton fibers (Kang et al. 2008). The adsorption capacity of the lignocellulosic material can be increased by physical and chemical modification of adsorbents. It is costly in nature at the industrial level. So, researchers are focusing on the use of low-cost adsorbents for the treatment operation.
Low-cost adsorbents
With the availability and cheapness of various waste materials, industrial by-products, agricultural wastes and other natural waste materials, the low-cost technique has become popular nowadays. The focus on selecting low-cost adsorbent is because of the high cost of commercially activated carbon. Researchers are preparing industrial by-products as low cost adsorbents, such as pulp and paper waste (Stniannopkao and Sreesai 2009), fertilizer waste (Gupta et al. 1997), steel converter slag (Mendez et al. 2009), steel making slag (Kim et al. 2008), sugarcane bagasse (Soliman et al. 2011), bagasse fly ash (Gupta and Ali 2000; Rao et al. 2002; Gupta et al. 2010) that are very common. Household wastes such as fruit waste (Kelly-Vargas et al. 2012), marine origin adsorbent such as peat (Brown et al. 2000; Márquez-Reyes et al. 2013) and red mud (Sahu et al. 2013; Bertocchi et al. 2006; Gupta et al. 2001) are also used in the treatment. Non-agricultural adsorbents are also used as low-cost adsorbents such as lignin (Betancur et al. 2009; Reyes et al. 2009), diatomic (Sheng et al. 2009), clino-pyrrhotite (Lu et al. 2006), aragonite shells (Kohler et al. 2007), natural zeolites (Apiratikul and Pavasant 2008), clay (Al-Jlil and Alsewailem 2009), kaolinite (Gu and Evans 2008) and peat (Liu et al. 2008).
Bioadsorbents
Mostly agricultural and plant wastes were used as bioadsorbents for wastewater treatment; these are very efficient and promising in the biosorption technique. There are generally three types based on the sources:(1) non-living biomass such as bark, lignin, shrimp, krill, squid, crab shell, etc.; (2) algal biomass; (3) microbial biomass, e.g., algae, bacteria, fungi and yeast.
Agricultural wastes in the preparation of bioadsorbents are also promising such as potato peel (Aman et al. 2008), sawdust (Ajmal et al. 1998; Kaczala et al. 2009), citrus peels (Schiewer and Patil 2008), mango peel (Iqbal et al. 2009a, b), corn cob (Leyva-Ramos et al. 2005; Vaughan et al. 2001), rice husk (Chockalingam and Subramanian 2006), tree fern (Ho 2003), wheat bran (Ozer and Ozer 2004), grape bagasse (Farinella et al. 2007), coconut copra meal (Ho and Ofomaja 2006), orange waste (Dhakal et al. 2005), walnut, hazelnut, almond shell (Pehlivan and Altun 2008), tea waste (Malkoc and Nuhoglu 2005), dried parthenium powder (Ajmal et al. 2006), sugarcane bagasse (Khan et al. 2001; Mohan and Singh 2002), pine needles (Dakiky et al. 2002), peanut shell (Namasivayam and Periasamy 1993), tamarind seeds (Gupta and Babu, 2009), sunflower stalk (Sun and Xu 1997) and black gram husk (Saeed et al. 2005).
Characterization of cellulosic waste material
Bioadsorbents are composed of mainly cellulose, hemicelluloses, lignin and extractives, and many other compounds such as lipid, starch, hydrocarbons, simple proteins and ash (Sud et al. 2008).
Cellulose
Cellulose (C5H8O4)m is a long linear polysaccharide polymer consisting of β-(1,4) linked glucose units. It is an important constituent of plant cell wall. It is present in plant cell combined with hemicelluloses and lignin. It is generally insoluble in water. The material with high cellulose contents are plant fibers, woods, stalks, stems, shells, straw, grasses, etc. (Table 1; Fig. 1).
Structure of cellulose (Chandra et al. 2012)
Hemicelluloses
Hemiceluloses (C5H8O4)m are another important constituent of plants materials. Hemicellulose is a dietary fiber consisting of a heterogenous group of polysaccharide substances that contain a number of sugars including xylose, mannose, galactose, arabinose and glucuronic acids. These are generally insoluble in water, but some hemicelluloses containing acids are water soluble. The materials with high hemicellulosic contents are barks, leaves, grasses, corn cobs, husks and shells (Table 1).
Lignin
Lignin [C9H10O3(OCh3) 0.9–1.7] n is a highly branched polymer consisting of phenol units which include trans-coniferyl, trans-sinapyl and trans-p-coumaryl. It is also insoluble in water and has both characteristics of dietary and functional fibers. It is mostly present in the stems, seeds of vegetables and fruits and cereals. The materials with high lignin contents are cereal material husks, others shells, leaves, barks, grasses and fruit seeds (Table 1).
Extractives
Extractives are organic materials and generally soluble in neutral solvents which includes resin, fats, alcohols, turpentine, tannins, fatty acids, waxes and flavonoids (Demirbas 2008a, b).
Properties of cellulosic low-cost adsorbents
Low-cost cellulosic biomass properties are generally proximate analysis, ultimate analysis and compositional properties. These properties show the variation of its constituents derived from different plant and agricultural waste.
Proximate properties
It generally shows the variation in fixed carbon, volatile matter, moisture and ash content in plant and agricultural materials (Table 2).
Ultimate properties
It gives the information about the elemental knowledge of a particular biomass followed by oxygen content, hydrogen content, nitrogen content and sulfur content (Table 3).
Compositional properties
The compositional properties of cellulosic adsorbents are characterrized with parameters like cellulose content, hemicelluloses content and lignin content.
Adsorption characteristics of cellulosic low-cost adsorbents
In the removal of metals from aqueous solution, different types of plant parts are used such as stems, stalks, leaves, husk, shells, roots, and barks and many others. These are freely and easily available, because India is rich in plant biomass. Agricultural plant materials are very common in the preparation of low-cost adsorbents. Most of the countries are rich in plant biodiversity and have large agricultural areas.
Husks
Rice is a crop that is cultivated all over the world. The hard outer covering of the grains of rice is a waste material generated from the rice milling process. In the world, rice is the major source of food calorie and livelihood. It is grown worldwide in most of the countries such as China, India and Indonesia. There is the problem of utilization of rice husk in rice-growing countries. Lignocellulogic agricultural waste material contains approximately 35 % cellulose, 25 % hemicelluloses, 20 % lignin, 17 % silica (including ash) and 3 % crude protein. It has been used widely in heavy metal removal from aqueous solutions (Ajmal et al. 2003; Bishnoi et al. 2004; Dadhlich et al. 2004). Sobhanardakani et al. 2013 applied untreated rice husk for removal of Cr(III) and Cu(II) from synthetic wastewater. He achieved the maximum sorption capacity of 22.5 and 30 mg/g, respectively. The adsorption capacities of different husk materials are in listed in Table 4.
It was reported that peanut husk modified with Fe and formaldehyde gives improve result. It was found that Fe-modified formaldehyde husk shows six times higher adsorption capacity than formaldehyde-modified peanut husk (Olguin et al. 2013). Wong et al. (2003) used tartaric acid-modified rice husk in the removal of Cu(II) and Pb(II) ions from aqueous solutions. He reported that the maximum metal uptake were found to be 29 and 108 mg/g at 27 °C for Cu(II) and Pb(II) metal ions, respectively. Fixed bed column study was also performed by the phosphate-treated rice husk in the removal of Pb(II), Cu(II), Zn(II) and Mn(II) at different time intervals. Table 5 (Mohan and Sreelakshmi 2008) describes the operating conditions for column experiments.
It was investigated that the flow rate 20 ml/min is optimum for the 10 mg/l solution. The breakthrough time was find to increase from 1.3 to 3.5 h for Pb(II), 4.0 to 9.0 h for Cu(II), 12.5 to 25.4 h for Zn(II) and 3.0 to 11.3 h for Mn(II) for increasing bed height up to 10–30 cm.
Straw and bran
The adsorbents prepared from straw and bran are commonly wheat straw and barley straw. Wheat straws have high worldwide production in some countries such as China, India and Russia. In 2013/14, the world wheat supplies increased from 5.3 million tons to 887.3 million tons (WASDE 2013). Wheat straw is commonly used mainly as cattle fodder. So it is needed to utilize wheat straw and bran for other applications also. The wheat straw is also lignocellulosic waste material that constitutes 34–40 % cellulose, 20–35 % hemicelluloses, 8–15 % lignin and sugars and other compounds (Keng et al. 2013). It was reported that wheat straw treated with microwave radiation gave significant results. It was found that the adsorption capacity was 39.22 mg/g (Farooq et al. 2011). The adsorption capacities of wheat straw and bran in heavy metal removal are given in Table 6.
Chojnacka (2006) investigated that ground straw removal of Cr(III) metal ions takes places when equilibrium is reached in less than 20 min. Farooq et al. (2011) found that wheat straw followed Langmuir model with maximum biosorption capacity (q max) mg/g. The maximum sorption occurred at pH 6 and the equilibrium time was 20 min. Barley husk showed the maximum sorption capacities of 69 and 88 % for Cu(II) and Pb(II), respectively (Pehlivan et al. 2009a, b, c). It was found that the favorable pH values for the removal of Cu(II) and Pb(II) were 6.0 and 6.6, respectively. The Langmuir isotherm model was fit with the sorption equilibrium results. The equilibrium sorption obtained after 2 h and the adsorption capacities for Cu(II) and Pb(II) were 4.64 mg/g and 23.20 mg/g, respectively (Pehlivan et al. 2009a, b, c).
Fruit peel/pulp
The tropical as well as temperate countries produce different types of fruits depending on climatic variations. The peels of different types of fruits are considered as fruit waste material that can be used for biosorption of heavy metals in different wastewater (Table 7). The apple pulps constitute 16 % cellulose, 16 % hemicelluloses and 21 % lignin (Cagnon et al. 2009). As biosorbent, orange peel indicates high metal adsorption potential due to its high content of cellulose, pectin (galacturonic acid), hemicelluloses and lignin (Feng et al. 2011). The adsorption of Cr(VI) ions from an aqueous solution of mosambi (sweet lime) peel dust has also been reported by Saha et al. 2013) without any prior modification. The adsorption of Cr(VI) was studied at different parameters such as sorbate concentration, pH, contact time and temperature with the highest adsorption capacity of 250 mg/g (Table 7) at pH 2.0 and 40 °C. The adsorption data was fit with the Langmuir isotherm that confirmed monolayer adsorption of hexavalent chromium on mosambi (sweet lime) peel.
Huang and Zhu (2013) prepared chemically modified biosorbent from muskmelon by the saponification process with alkaline solution of Ca(OH)2. They reported that the optimum equilibrium pH range for 100 % adsorption 4–6.4. They also revealed the factor responsible for the uptake of metal ions was pectic acid present in muskmelon peel. The maximum adsorption capacities were found to be 0.81 mol/kg for Pb(II) ions at equilibrium time of up to 10 min. The use of sugar beet pulp for Cr(IV) removal was studied by Altundogan et al. (2007). The adsorbent was treated with sulfuric acid medium and sulfur dioxide gas reactant. The lower pH (2–3) was reported with the 24 mg/g adsorption capacities at 25 °C.
Bagasse
In the plant waste, bagasse is a very common waste material that was generated from the sugarcane industry as by-products (Table 8). It was used by Alomá et al. (2012) in the removal of Ni(II) ions from the aqueous solution. The adsorption capacity for Ni(II) ion removal at pH 5 at 25 °C was evaluated. The calculated sorption capacity was approximately 2 mg/g. Adsorption followed Langmuir, Freundlich and sips isotherm models. They also reported that the Langmuir model represented data in a better way, with correlation coefficient greater than 0.95.
Yu et al. (2013) used sugarcane bagasse modified with PMDA and unmodified form for the removal of heavy metals such as Pb2+, Cd2+, Cu2+ and Zn2+. It was found that adsorption of these four metal ions increased with an increasing solution pH and dosages. Langmuir isotherm model fit with equilibrium results. The adsorption capacities of modified bagasse were 1.06, 0.93, 1.21 and 1.0 mmol/g and for unmodified bagasse 0.04, 0.13, 0.10, and 0.07 mmol/g for Pb2+, Cd2+, Cu2+ and Zn2+, respectively. FTIR and EDX studies also performed showed that the adsorption mechanism and kinetic process, pseudo-first order and pseudo-second order were also used to predict the adsorption rates.
Stalk
Plant stalks are cellulosic materials consisting of cellulose, hemicelluloses and lignin. Many plant stalk such as corn stalk (Zheng et al. 2012) and sunflower stalk (Sun and Shi 1998) are used for the removal of toxic metals (Table 9). Corn stalk as adsorbent was used after modification by graft polymerization for the removal of Cd(II) metal ion from aqueous solution (Zheng et al. 2012). The maximum adsorption of Cd(II) metal ion was found to be 21.37 mg/g. They also reported that modified corn stalk had better potential of metal ion removal than unmodified corn stalk because of the addition of functional groups (–CN and –OH groups) and the lower crystallinity. Scanning electron microscopy (SEM), energy dispersive spectroscopy (SEM–EDS, X-ray diffraction (XRD) and solid-state CP/MAS C13 NMR were used for characterization of adsorbents.
The feasibility of sunflower stalks for lead (Pb) and cadmium (Cd) metal ion adsorption has been investigated by Jalali and Aboulghazi (2013). Batch adsorption studies were conducted to study the effect of contact time, initial concentration (50 mg/l), pH (4–9) and adsorbent doses (0.2–1.2 g) on the removal of Cd(II) and Pb(II) metal ions at room temperature. The data fitted well with the modified two-site Langmuir model with maximum sorption capacities for Pb(II) and Cd(II) at optimum conditions of 182 and 70 mg/g. The pseudo-second-order kinetic model fitted well with the rate constant 8.42 × 10−12 and 8.95 × 102 g/mg/m for Cd and Pb, respectively.
Shell
The effectiveness of lignocellulosic material as adsorbent from aqueous solution is due to the affinity between water molecule and cell wall components. These materials are highly porous and have a wide surface area. In the bioadsorbents as shell, coconut, bael fruit, cashew nut, oil palm, wheat and wood apple nd many others are used for various heavy metal removal (Table 10).
The biosorption of Pb(II) ions using hazelnut shells (NHS) and almond shells (AS) was investigated in batch experiments. Alkaline pH (6–7) was found to be favorable for the removal of metal ions. The uptake capacities were found to be 90 and 68 % for NHS and AS sorbents after 90 min equilibrium time. The adsorption isotherm for Pb(II) fitted well with the Langmuir model, with binding capacities of shell of 28.18 and 8.08 mg/g for NHS and AS, respectively. Doke and Khan (2012) also used H2SO4-modified wood apple shell for the adsorption of Cr(VI) metal in aqueous medium. The maximum adsorption capacity was 151.51 mg/g which is the highest of other shell adsorbents. Oil palm shell was evaluated as a adsorption for the removal of Cu(II) from synthetic wastewater by Chong et al. 2013. An adsorption capacity of 1.756 mg/g was reported for Cu(II). They also used the same adsorbent for Pb(II) removal and reported an adsorption capacity of 3.309 mg/g for Pb(II) metal ion. The material was used for both batch mode and column mode studies. They found that the lower pHPZC(4.1) is suitable for heavy metal removal at optimum conditions. The Freundlich isotherm was fitted well than Langmuir isotherm. The kinetics of Pb(II) adsorption follow pseudo-second-order kinetic model.
Leave
Lignocellulosic materials are the structural elements of wood and other plant materials. These are present in the biosphere in abundant form. Leaves come in the category of natural materials. Most of the plants shed their leaves in unfavorable conditions and these leaves can be used as biosorbents (Table 11). The removal of Cu(II) from aqueous solution using dried sunflower leaves was investigated by Benaïssa and Elouchdi (2007). The influence of initial Cu(II) concentrations (10–500 mg/l), pH (5–6), contact time (2.5–7 h) and adsorption amount (0.2 g) was observed. The experimental data were well followed by Langmuir and Freundlich isotherms. The kinetic model and pseudo-first-order also supports the rate of reaction. The maximum metal ion uptake capacities obtained was 89.37 mg/g. Martins et al. (2013) used castor leaf powder as bioadsorbent for the removal of C(II) and Pb(II) metals from an aqueous medium. The adsorption capacities were found to be 0.340 and 0.327 mmol/g for C(II) and Pb(II) metals, respectively.
Mondal et al. (2013) used bamboo leaf powder in the detoxification of Hg(II) ions from water. They used bamboo leaf powder in three forms, viz., unmodified bamboo leaf powder (BPL), modified by using anionic surfactant SDS (BLPS) and non-ionic surfactant Triton X-100 (BLPT). All these materials were characterized by BET and FTIR analysis. The experimental studies were supported by the adsorption isotherm, kinetics, thermodynamics and the mechanisms involved in it. The maximum adsorption capacity shown by unmodified, Triton X-modified and SDS-modified BPL was 27.11, 28.1 and 35.05 mg/g, respectively. Very little literature investigation has been done on the use of pine needles (or leaf) in heavy metal removal. Pine needle is novel emerging adsorbent which was examined by Shafique et al. (2012) used chir pine leaves (Pinus roxburghii) in the removal of As(V) ions from aqueous solution. The maximum adsorption was reported at pH 4.0 and equilibrium was achieved in 35 min. The pine leaves were tested for various contact times, pH, agitation speed and initial metal concentration to evaluate the optimum conditions which showed the maximum As(V) metal ions uptake of 3.27 mg/g. The experiment was further supported by pseudo-second-order kinetics.
Bark
Plant’s bark is also used for heavy metal removal in aqueous solution (Table 12). Different concentrations of Cr(VI) and Cr(III) ions were studied by Sarin and Pant 2006. They used eucalyptus bark in the removal of Cr(VI) and Cr(III) metal ions. The experimetal study was performed in a batch process and the influence of the following parameters, pH, contact time and initial concentration, will be investigated. The adsorption was followed by Fruendlich isotherms mainly and first-order Lagergren kinetics. The adsorption capacity was found to be 45 mg/g at pH 2.
Alkali NaOH- and acid H2SO4-pretreated neem barks were used as adsorbent and the influence of initial cation concentration, temperature and pH was investigated to optimize Zn(II) and Cd(II) metal ion removal from aqueous solutions (Naiya et al. 2009). The maximum adsorption capacity was obtained as 13.29 for Zn(II) ion and 25.57 mg/g for Cd(II) ion at pH 5 for Zn(II) and 6 for Cd(II), respectively. Different parameters such as pH, initial ion concentration, contact time and adsorbent doses were studied to evaluate the equilibrium conditions. Thermodynamic parameters and Gibbs free energy (∆G) values for Zn(II) are −4.76 KJmol−1 and for Cd(II) are −6.09 KJmol−1, respectively, were also studied. Reddy et al. (2011) also used Moringa oleifera bark as low-cost adsorbents for the biosorption of Ni(II) metal from aqueous solution. The adsorption capacity was found to be 30.38 mg/g at 6 pH.
Fiber
In 2010, the removal of heavy metals from wastewater by using Agave Americana fibers was studied by Hamissa et al. 2010. It was indicated that Agave Americana fiber is more effective for Pb(II) and Cd(II) is also exchanged at a satisfactory level. Approximately, 40.0 mg/g of Pb(II) and 12.5 mg/g of Cd(II) were removed. The equilibrium conditions were obtained at 20 °C temperature, pH 5.0, contact time of 30–60 min and 5 g/l biomass adsorbent media. Infrared scopy revealed that the functional groups were involved in Pb(II) and Cd(II) ion bins on adsorbent media. Scanning electron microscopy (SEM) also gives proof of the adsorption surface area. Thermodynamic parameters such as enthalpy change (∆Ho), free energy change (∆Go) and entropy change (∆So) were calculated from Langmuir and Freundlich isotherm constant. The positive value of ∆H o indicates that the sorption process is endothermic in nature. Hydrogen peroxide-modified coir was also used in metal removal from aqueous solutions. It was found that coir fibers with chemical modification were found to be more effective than unmodified coir fibers. Heavy metals such as Ni(II), Zn(II) and Fe(II) could be eliminated with a removal capacity of 4.33, 7.88 and 7.49 mg/g for chemically modified adsorbents, respectively, and unmodified coir fiber uptake capacity were 2.51, 1.53 and 2.84 mg/g. It was also found that metal capacity decreases with lowering of pH. Desorption study was also carried with dilution of NaOH solution with loaded metal ions (Shukla et al. 2006). It was reported the adsorption process decreased with lowering of pH and the Langmuir model fitted for modified jute fibers. Plant fibers such as those of Agave americana, kenaf, coir, banana, remie and jute were used for heavy metal removal (Table 13).
In 2005, the use of modified jute fibers to remove heavy metals was investigated (Shukla and Pai 2005). It was observed that modified jute fibers were used in the synthetic waste water containing toxic heavy metals, viz., Cu(II), Ni(II) and Zn(II). They used two types of fibers in the metal ion sequestration. The dye-loaded jute fibers showed the metal uptake value of 8.4, 5.26 and 5.95 mg/g for Cu(II), Ni(II) and Zn(II), respectively. The other adsorbent modified with hydrogen peroxide showed the metal uptake values of 7.73, 3.37 and 3.55 mg/g for unmodified jute fibers.
Fruit stone/waste
Fruit containing stones (stone fruit) are used adsorbent for metal removal after removing their central fleshy parts. Peach stones, olive stones and palm fruit bunches’ inner and outer hard parts are used as adsorbents for metal removal. The raw material obtained from the fruit stone part is dried and washed with organic solvents (Ali 2014). Rashed (2006) carried out a comparative study of fruit stones (peach and apricot) and found their adsorption potential. The equilibrium time for lead adsorption was 3–5 h (%Pb adsorption 93 % for apricot and 97.64 % for peach). The lead adsorption onto peach stone was found to be higher than onto stone up to 3.36 % at 3 h. The suitable pH was observed to be 7–8. The heavy metal removal capacities of fruit stone/waste are shown in Table 14.
Alslaibi et al. (2013) determined the potential of microwaved olive stone-activated carbon (OSAC) for removal of cadmium metal ion. The maximum cadmium uptake obtained using OSAC was 95.32 %. The adsorption process was followed by Langmuir isotherm with 11.72 mg/g adsorption capacity. Mohammadi et al. (2010) examined the efficacy of modified sea-buckthorn stone to adsorb Pb(II) metal ions. Activated carbons have been prepared using phosphoric acid and zinc chloride chemical activation. The maximum adsorption of Pb(II) on activated carbon was 51.81 mg/g with H3PO4 and 25.91 mg/g with activated ZnCl2.
Peat
Peat moss is used as an inexpensive and naturally available low-cost adsorbent. Lignin and cellulose are the chief components of peat. Due to having polar functional groups, peat works effectively in metal detoxification from aqueous solutions. Ho and Mckay (2004) investigated sorption of Cu(II) by peat moss. The adsorption was maximum at pH 5, and the maximum adsorption capacity was 0.199 mmol/g at 20 °C. The mechanism behind Cu(II) uptake was cation exchange. The cupper ion was exchanged with hydrogen ions in the presence of humic and fulvic acids. Gupta et al. (2009) described adsorption of Cu and Ni ions onto Irish peat moss. The adsorption of Cu(II) and Ni(II) from aqueous solutions on peat moss was studied over a range of 2–8 (pH) and 5–100 mg/l (concentration). The maximum biosorption capacity of Iris peat moss was found to be 17.6 mg/g for Cu(II) and 14.5 mg/g for Liu et al. (2009) studied the use of peat for removal of nickel from aqueous solutions at different pH values. It was observed that metal ion removal increases with increase in pH value. The first-order model favored the experimental data. Table 15 represents the metal removal capacities of different types of peat biomass.
Janaki et al. (2015) reported the removal of Ni(II) ions from an aqueous solution of Indian peat moss (sphagnum) as adsorbent. The effects of pH, adsorbent dosage and initial concentrations were studied in batch experiment. The experimental results revealed that 99.5 % of Ni(II) ion removal occurs at pH 6. The authors also described the interaction between the metal ions and peat mosses by Fourier transform infrared spectroscopy.
Vegetable waste
The applicability of vegetable waste as low-cost adsorbent leads to zero waste discharge in the environment. Vegetable wastes are easily available and have no economic use (Table 16). Gill et al. (2013) reported the removal of Ni(II) onto a mixture of vegetable waste as adsorbent. The mixture of vegetable waste was prepared in the ratio of 1:1 (potato:carrot peels). The effects of various operating variables, viz., initial pH, temperature, contact time, initial metal concentration and biosorbent dose, were studied. The maximum adsorption of nickel (79.32 %) was found with 75 min of contact time and 3.0 g of biosorbent at 35 °C and ph 4. FTIR spectrophotometer and X-ray flourescence spectrophotometer techniques confirm the adsorption process. Bhatti et al. (2010) studied the adsorption of chromium on Daucus carota L. waste biomass. The maximum removal capacity for Cr(III) and Cr(VI) was 85.65 and 88.27 mg/g, respectively. The maximum removal rate occurred at biosorbent dose 0.1 g, biosorbent size 0.250 mm, initial concentration 100 mg/l, temperature 30 °C and contact time 240 min.
Aksu and Isoglu (2005) examined the biosorption equilibria and kinetics of copper(II) metal ion via agricultural waste sugar beet pulp. The highest biosorption capacity was 28.5 mg/g for Cu(II) at 25 °C and initial pH value 4. The biosorption rates were found to follow pseudo-first order and pseudo-second order.
Grass
Grass is considered to be of low cost and abundant because of mowing lawns, gardens, parks and open fields (Table 17). Grasses are major organic components of solid waste and comprise about 14.6 % of total municipal solid waste (MSW) and about 50 % organic content of the MSW (Yu et al. 2002). Koroki et al. (2010) used culm of bamboo grass treated with concentrated sulfuric acid for Cr(V) metal ion removal from aqueous solutions. They found that the Cr(VI) requestration was highly correlated with pH and favored physicochemical sorption mechanism. The Cr(VI) sorption was observed irreversible due to strong bonding of HCrO4 − and the presence of active sites. Zuo et al. (2012) tried to evaluate the applicability of sodium hydroxide solution (NaOH) immersed lemon grass (ILG) for the removal of cupper(Cu), zinc(Zn) and cadmium(Cd) from single and multi-metal solutions. According to the authors, maximum removal was 13.93 mg Cu, 15.87 mg Zn and 39.53 mg Cd per gram ILG. FTIR studies showed that NaOH modification leads to increase in the number of sorption sites for metal uptake.
Pandey et al. (2015) explored NaOH-treated kush grass leaves and bamboo leaves for Cd(II) removal from aqueous media. NaOH-modified Desmostachya bipinnata, Kush grass leaves (MDBL) and Bambusa arundinacea (bamboo) leaves (MBAL) were used in batch experiments. Langmuir isotherm fitted well than Freundlich isotherm and the maximum adsorption capacity was found to be 15.22 mg/g for MBDL and 19.70 mg/g for MBAL at room temperature. Desorption studies were also carried out using 0.1 N HNO3; 94.18 and 92.98 % recovery of metals was obtained for Cd(II) ions from MDBL and MBL, respectively. Hossain et al. (2012) utilized garden grass (GG) for removal of copper(II) from aqueous solutions. The maximum adsorption and desorption capacities were 58.34 and 319.03 mg/g, respectively, for 1 g dose. From the results, it was revealed that GG occupied high surface area and functional groups on the surface area.
Cake
The cakes of olive, cotton seed and jatropha are agricultural wastes and applied as cellulosic adsorbents for heavy metal removal (Table 18). Malathi et al. (2015) examined the ability of activated carbon prepared from sulfuric acid-treated cottonseed cake (SCSC) by chemical activation. According to the authors, the equilibrium time and optimum pH range were observed to be 3 h and 4.0–6.0, respectively. SCSC exhibit a higher adsorption capacity of 115.86 mg/g than commercial activated carbon (21.69 mg/g) at 300 K. Bose et al. (2011) evaluated a biodiesel waste of jatropha seed press cake (JPC) for the elimination of hexavalent chromium ion from aqueous solutions. The chromium metal removal increases with increase in pH as well as concentration. The peak biosorption capacity was observed at 22.727 mg of Cr(VI)/g of biosorbent at 30 °C. The activation energy for the adsorption process was 27.114 kJ/mol, showing a physical process.
Konstantinou et al. (2007) investigated the sorption ability of olive cake for Cu(II) and Eu(II) ions in a batch study. They observed that the sorption process takes place due to formation of an inner-sphere complex with active sites of the surface. Elouear et al. (2008) studied the removal of toxic metal ions from aqueous solutions using exhausted olive cake ash (EOCA). The optimum removal occurred up to 2 h contact time for Ni(II) and Cd(II) onto EOCA at pH 6. Langmuir isotherm correlated well than Freundlich isotherm. The adsorption capacities were 8.34 and 7.32 mg/g for Ni(II) and Cd(II), respectively. Khan et al. (2012) utilized oil cake in the removal of nickel from aqueous medium. Metal removal favored pseudo-second order model. The breakthrough capacities for 5 and 10 mg/l were 0.25 and 4.5 mg/g and exhausted capacities for 5 and 10 mg/l were 4.5 and 9.5 mg/g for Ni(II) metal ion, respectively.
Others adsorbents
Different cellulosic material used in the removal of heavy metals such as cactus cladodes, castor seed hull, Eichhornia crassipes roots, hemp fibers, meranti wood and Prosopis juliflora seed were found to be efficient as low-cost bioadsorbents (Table 19).
Conclusion
Adsorption is an efficient technique in heavy metal removal rather than coagulation, flocculation, ion exchange, precipitation, osmosis and flotation. These conventional techniques are not suitable for the removal of heavy metal ions from wastewater at trace concentrations. The use of commercially activated carbons for wastewater treatment leads to increase in the cost of treatment, and, hence, researchers are focusing on the use of feasible cellulosic low-cost adsorbents for metal adsorption. Cellulosic waste materials are promising adsorbents for wastewater treatments, because of their abundance and renewability. Most of these cellulosic wastes are rich in cellulose, hemicelluloses and lignin content which adhere to toxic pollutants on the surface. In this review, the emerging cellulosic low-cost adsorbents are utilized for the removal of various kinds of metals from different types of aqueous solutions. It is evident that most of the cellulosic adsorbents applied for metal sequestration exhibited efficient adsorption capacity. So, these materials can serve as an alternative to commercially available activated carbons. Further research requires investigation of structural studies of adsorbents, multi-metal studies, immobilization of adsorbent, reuse of adsorbent, recovery of metals and pilot-scale studies.
References
Abbas M, Kaddour S, Trari M (2014) Kinetic and equilibrium studies of cobalt adsorption on apricot stone activated carbon. J Ind Eng Eng Chem 20(3):745–751
Abbasi T, Abbasi SA (2010) Biomass energy and the environmental impacts associated with its production and utilization. Renew Sustain Energy Rev 14:919–937
Adebowale KO, Unuabonah IE, Olu-Owolabi BI (2006) The effect of some operating variables on the adsorption of lead and cadmium ions on kaolinite clay. J Hazard Mater 134:130–139
Ahmad AL, Ooi BS (2010) A study on acid reclamation and copper recovery using low pressure nanofiltration membrane. Chem Eng J 56:257–263
Ajmal M, Khan AH, Ahmad S, Ahmad A (1998) Role of sawdust in the removal of copper (II) from industrial wastes. Water Res 22:3085–3091
Ajmal M, Rao RAK, Ahmad R, Ahmad J (2000) Adsorption studies on Citrus reticulate (fruit peel of orange): removal and recovery of Ni(II) from electroplating wastewater. J Hazard Mater 79:117–131
Ajmal M, Rao RAK, Anwar S, Ahmad J, Ahmad R (2003) Adsorption studies on rice husk: removal and recovery of Cd(II) from wastewater. Bioresour Technol 86(2):147–149
Ajmal M, Rao RAK, Ahmad R, Khan MA (2006) Adsorption studies on Parthenium hysterophrous weed: removal and recovery of Cd (II) from wastewater. J Hazard Mater B135:242–248
Aksu Z, Isoglu IA (2005) Removal of copper(II) ions from aqueous solution by biosorption onto agricultural waste sugar beet pulp. Process Biochem 40(9):3031–3044
Ali I (2014) The quest for active carbon adsorbent substituted: inexpensive adsorbent for toxic metal ions removal from wastewater. Sep Purif Rev 39(3–4):97–171
Al-Jlil SA, Alsewailem FD (2009) Saudi Arabian clays for lead removal in wastewater. Appl Clay Sci 42:671–674
Alomá I, Martín-Lara MA, Rodríguez IL, Blázquez G, Calero M (2012) Removal of nickel (II) ions from aqueous solutions by biosorption on sugarcane bagasse. J Taiwan Inst Chem E 43:275–281
AL-Othman ZA, Ali R, Naushad MU (2012) Hexavalent chromium removal from aqueous medium by activated carbon prepared from peanut shell:Adsorption kinetics, equilibrium and thermodynamic studies. Chem Eng J 184:238–247
Al-Rashdi B, Samerfield C, Hilal N (2011) Heavy metals removal using adsorption and nanofiltration techniques. Sep Purif Rev 40:209–259
Alslaibi TM, Abustan I, Ahmad MA, Foul AA (2013) Cadmium removal from aqueous solution using microwaved olive stone activated carbon. J Environ Chem Eng 1(3):589–599
Altundogan SH, Bahar N, Mujde B, Tumen F (2007) The use of sulphuric acid-carbonization products of sugar beet pulp in Cr(VI) removal. J Hazard Mater 144(1–2):255–264
Alyüz B, Veli S (2009) Kinetics and equilibrium studies for the removal of nickel and zinc from aqueous solutions by ion exchange resins. J Hazard Mater 167:482–488
Aman T, Kazi AA, Sabri MU, Bano Q (2008) Potato peels as solid waste for the removal of heavy metal copper(II) from waste water/industrial effluent. Colloid Surf 63:116–121
Anandkumar J, Mandal B (2009) Removal of Cr(VI) from aqueous solution using Bael fruit (Aegle marmelos correa) shell as an adsorbent. J Hazard Mater 168:633–640
Apiratikul R, Pavasant P (2008) Sorption of Cu2+, Cd2+, and Pb2+ using modified zeolite from coal fly ash. Chem Eng J 144:245–258
Aydin H, Buluta Y, Yerlikayab C (2008) Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents. J Environ Manage 87:37–45
Aziz HA, Adlan MN, Ariffin KS (2008) Heavy metals (Cd, Pb, Zn, Ni, Cu and Cr(III)) removal from water in Malaysia: post treatment by high quality limestone. Bioresour Technol 99:1578–1583
Babarinde NAA, Babalola JO, Sanni RA (2006) Biosorption of lead ions from aqueous solution by maize leaf. Intl J Phys Sci 1(1):23–26
Babel S, Kurniawan TA (2004) Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial activated carbon modified with oxidizing agents and/or chitosan. Chemosphere 54:951–967
Babu BV, Gupta S (2008) Adsorption of Cr(VI) using activated neem leaves: kinetic studies. Adsorption 14:85–92
Barakat MA (2011) New trends in removing heavy metals from industrial wastewater. Arab J Chem 4:361–377
Barka N, Abdennouri M, El Makhfouk M, Qourzal S (2013) Biosorption characteristics of cadmium and lead onto eco-friendly dried cactus (Opuntia ficus indica) cladodes. J Environ Chem Eng 1(3):144–149
Barrera H, Ureńa-Núńez F, Bilyeu B, Barrera-Díaz C (2006) Removal of chromium and toxic ions present in mine drainage by ectodermis of opuntia. J Hazard Mater 136:846–853
Basaldella EI, Vazquez PG, Iucolano F, Caputo D (2007) Chromium removal from water using LTA zeolites: effect of pH. J Colloid Interface Sci 313:574–578
Benaïssa H, Elouchdi MA (2007) Removal of copper ions from aqueous solution by dried sunflower leaves. Chem Eng Process 46:614–622
Bertocchi AF, Ghiani M, Peretti R, Zucca A (2006) Red mud and fly ash for mine site contaminated with As, Cd, Cu, Pb and Zn. J Hazard Mater 134:112–119
Betancur M, Bonelli PR, Velásquez JA, Cukierman AL (2009) Potentiality of lignin from the kraft pulping process for removal of trace nickel from wastewater: effect of demineralization. Bioresour Technol 100:1130–1137
Bhatti HN, Nasir AW, Hanif MA (2010) Efficacy of Daucas carota L. waste biomass for the removal of chromium from aqueous solutions. Desalination 253(1–3):78–87
Bishnoi NR, Bajaj M, Sharma N, Gupta A (2004) Adsorption of Cr(VI) on activated rice husk carbon and activated alumina. Bioresour Technol 91:305–307
Bose A, Kavitha B, Keharia H (2011) The suitability of jatropha seed press cake as a biosorbent for removal of hexavalent chromium from aqueous solutions. Bioremediat J 15(4):218–229
Bratskaya SY, Pestov AV, Yatluk YG, Avramenko VA (2009) Heavy metals removal by flocculation/precipitation using N-(2-carboxyethyl)chitosans. Colloid Surf 339:140–144
Brown PA, Gill SA, Allen SJ (2000) Metal removal from wastewater using peat. Water Res 34(16):3907–3916
Buasri A, Chaiyut N, Tapang K, Jaroensin S, Panphrom S (2012) Equilibrium and kinetic studies of biosorption of Zn(II) ions from wastewater using modified corncob. APCBEE Procedia 3:60–64
Cagnon B, Py X, Guillot A, Stoeckli F, Chambat G (2009) Contributions of hemicellulose, cellulose and lignin to the mass and the porous properties of chars and steam activated carbons from various lignocellulosic precursors. Bioresour Technol 100:292–298
Chandra R, Takeuchi H, Hasegawa T (2012) Methane production from lignocellulosic agricultural crop wastes: a review in context to second generation of biofuel production. Renew Sustain Energy Rev 16:1462–1476
Chang Q, Wang G (2007) Study on the macromolecular coagulant PEX which traps heavy metals. Chem Eng Sci 62:4636–4643
Chang Q, Zhang M, Wang JX (2009) Removal of Cu2+ and turbidity from wastewater by mercaptoacetyl chitosan. J Hazard Mater 169:621–625
Chen H, Han Y, Xu J (2008) Simultaneous saccharification and fermentation of steam exploded wheat straw pretreated with alkaline peroxide. Process Biochem 43:1462–1466
Chockalingam E, Subramanian S (2006) Studies on removal of metal ions and sulphate reduction using rice husk and Desulfotomaculum nigrificans with reference to remediation of acid mine drainage. Chemosphere 62:699–708
Chojnacka K (2006) Biosorption of Cr(III) ions by wheat straw and grass: a systematic characterization of new biosorbents. Pol J Environ Stud 15:845–852
Chong HLH, Chia PS, Ahmad MN (2013) The adsorption of heavy metal by Bornean oil palm shell and its potential application as constructed wetland media. Bioresour Technol 130:181–186
Cifuentes L, García I, Arriagada P, Casas JM (2009) The use of electrodialysis for metal separation and water recovery from CuSO4-H2SO4-Fe solutions. Sep Purif Technol 68:105–108
Cséfalvay E, Pauer V, Mizsey P (2009) Recovery of copper from process waters by nanofiltration and reverse osmosis. Desalination 240:132–142
Dakiky M, Khamis M, Manassra A, Mereb M (2002) Selective adsorption of chromium (VI) in industrial wastewater using low-cost abundantly available adsorbents. Adv Environ Res 6:533–540
Dadhlich AS, Beebi SK, Kavitha GV (2004) Adsorption of Ni(II) using, rice husk. J Environ Sci Eng 46:179–185
Daneshwar N, Salari D, Aber A (2002) Chromium adsorption and Cr(VI) reduction to trivalent chromium in aqueous solution by soya cake. J Hazard Mater B94:49–60
Dang VBH, Doan HD, Dang-Vu T, Lohi A (2009) Equilibrium and kinetics of biosorption of cadmium (II) and copper (II) ions by wheat straw. Bioresour Technol 100:211–219
Demiral H, Demiral I, Karabacakoglu B, Tumsek F (2011) Production of activated carbon from olive bagasse by physical activation. Chem Eng Design 89:206–213
Demirbas A (2004) Combustion characteristics of different biomass fuels. Prog Energy Combust Sci 30:219–230
Demirbas A (2008a) The sustainability of combustible renewables. Energy sources A 30(12):1114–1119
Demirbas E (2008b) Heavy metal adsorption onto agro-based waste materials: a review. J Hazard Mater 157:220–229
Demirbas A (2009) Biorefineries: current activities and future developments. Energy Convers Manage 50:2782–2801
Dhakal RP, Ghimire KN, Inoue K (2005) Adsorptive separation of heavy metals from an aquatic environment using orange waste. Hydrometallurgy 79:182–190
Dhir B, Kumar R (2010) Adsorption of heavy metals by salvinia biomass and agricultural residues. Int J Environ Res 4:427–432
Dialynas E, Diamadopoulos E (2009) Integration of a membrane bioreactor coupled with reverse osmosis for advanced treatment of municipal wastewater. Desalination 238:302–311
Doke KM, Khan EM (2012) Equilibrium, kinetic and diffusion mechanism of Cr(VI) adsorption onto activated carbon derived from wood apple shell. Arab J Chem. doi:10.1016/j.arabjc.2012.07.031 (article in press)
Duan JC, Lu Q, Chen RW, Duan YQ, Wang LF, Gao L, Pan SY (2010) Synthesis of a novel flocculant on the basis of crosslinked Konjac glucomannan-graftpolyacrylamide-co-sodium xanthate and its application in removal of Cu2+ ion. Carbohydr Polym 80:436–441
El Samrani AG, Lartiges BS, Villiéras F (2008) Chemical coagulation of combined sewer overflow: heavy metal removal and treatment optimization. Water Res 42:951–960
Elouear Z, Bowid J, Boujelben N, Feki M, Montiel A (2008) The use of exhausted olive cake ash (EOCA) as a low cost adsorbent for the removal of toxic metal ions from aqueous solutions. Fuel 87:2582–2589
Erikson P (1988) Nanofiltration extends the range of membrane filtration. Environ Prog 7:58–61
Farajzadeh MF, Monji AB (2004) Adsorption characteristics of wheat bran, towards heavy metal cations. Sep Sci Technol 38:197–207
Farinella NV, Matos GD, Arruda MAZ (2007) Grape bagasse as a potential biosorbent of metals in effluent treatments. Bioresour Technol 98:1940–1946
Farinella NV, Matos GD, Lehman EL, Arruda MAZ (2008) Grape bagasse as an alternative natural adsorbent of cadmium and lead for effluent treatment. J Hazard Mater 154(1–3):1007–1012
Farooq U, Khan MA, Atharc M, Kozinskia JA (2011) Effect of modification of environmentally friendly bioadsorbents wheat (Triticum aestivum) on the biosorptive removal of cadmium(II) ions from aqueous solution. Chem Eng J 171:400–410
Faust SD, Aly OM (1987) Adsorption processes for water treatment. Butterworth Publishers, Stoneham
Feng N, Guo X, Liang S, Zhu Y, Liu J (2011) Biosorption of heavy metals from aqueous solutions by chemically modified orange peel. J Hazard Mater 185:49-54
Feng J, Hong QY, Green AES (2006) Analytical model of corn cob pyroprobe-FTIR data. Biomass Bioenerg 30:486–492
Fernandez Y, Maranon E, Costrillon L, Vazquez I (2005) Removal of Cd and Zn from inorganic industrial waste leachate by ion exchange. J Hazard Mater 126(1–3):169–175
Figoli A, Cassano A, Criscuoli A, Mozumder MSI, Uddin MT, Islam MA, Drioli E (2010) Influence of operating parameters on the arsenic removal by nanofiltration. Water Res 44:97–104
Fiol N, Villaescus I, Martinez M, Miralles N, Poch J, Serarols J (2006) Sorption of Pb(II), Ni(II), Cu(II), and Cu(II) from aqueous solution by olive stone waste. Sep Purif Technol 50:132–140
Fu F, Wang Q (2011) Removal of heavy metal ions from wastewaters: a review. J Environ Manag 92:407–418
Gamage A, Shahidi F (2007) Use of chitosan for the removal of metal ion contaminants and proteins from water. Food Chem 104(3):989–996
Gill R, Mahmood A, Nazir R (2013) Biosorption potential and kinetic studies of vegetable waste mixture for the removal of nickel(II). J Hazard Mater Cycle Waste Manag 15:115–121
Grover PD, Iyer PVR, Rao TR (2002) Biomass-thermochemical characterization, 3rd edn. IIT Delhi MNES
Gu XY, Evans LJ (2008) Surface complexation modelling of Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) adsorption onto kaolinite. Geochim Cosmochim Acta 72:267–276
Guechi EK, Hamdaowio O (2015) Evaluation of potato peel as a novel adsorbent for the removal of Cu(II) from aqueous solutions: equilibrium, kinetics and thermodynamic studies. Desalinat Water Treat 57(23):10677–10688
Gundogdu A, Ozdes D, Duran C, Bulut VN, Soylak M (2009) Biosorption of Pb(II)ions from aqueous solution by pine bark (Pinus brutia Ten). Chem Eng J 153:62–69
Guo MX, Qiu GN, Song WP (2010) Poultry litter-based activated carbon for removing heavy metal ions in water. Waste Manage 30:308–315
Gupta VK, Ali I (2000) Utilization of bagasse fly ash (a sugar industry waste) for the removal of copper and zinc from wastewater. Sep Purif Technol 18:131–140
Gupta S, Babu BV (2009) Utilization of waste product (tamarind seeds) for the removal of Cr(VI) from aqueous solutions: equilibrium, kinetics, and regeneration studies. J Environ Manag 90:3013–3022
Gupta VK, Gupta M, Sharma M (2001) Process development for the removal of lead and chromium from aqueous solution using red mud—an aluminium industry waste. Water Res 35(5):1125–1134
Gupta BS, Curran M, Hosan S, Ghos TK (2009) Adsorption characteristics of Cu and Ni on Irish peat moss. J Env Manag 90:954–960
Gupta VK, Rastogi A, Nayak A (2010) Adsorption studies on the removal of hexavalent chromium from aqueous solution using a low cost material. J Colloid Interface Sci 342(1):135–141
Gupta VK, Srivastava SK, Mohan D, Sharma S (1997) Design parameters for fixed bed reactors of activated carbon developed from fertilizers waste for the removal of some heavy metal ions. Waste Manag 17(8):517–522
Hamissa AMB, Lodi A, Seffen M, Finocchio E, Botter R, Converti A (2010) Sorption of Cd(II) and Pb(II) from aqueous solutions onto Agave americana fibers. Chem Eng J 159:67–74
Hanra MS, Ramchandran V (1996) Trace level separation of zinc sulphate and lead nitrate from toxic effluent streams by reverse osmosis modular systems. Sep Sci Technol 31(1):49–61
Heidmann I, Calmano W (2008) Removal of Zn(II), Cu(II), Ni(II), Ag(I) and Cr(VI) present in aqueous solutions by aluminium electrocoagulation. J Hazard Mater 152:934–941
Henryk K, Jaraslaw C, Witold Z (2016) Peat and coconut fiber as biofilters for chromium adsorption from contaminated wastewaters. Environ Sci Pollut Res 23:527–534
Ho YS (2003) Removal of copper ions from aqueous solution by tree fern. Water Res 37:2323–2330
Ho YS, Mckay G (2004) Sorption of copper(II) from aqueous solution by peat. Water Air Soil Pollut 158:77–97
Ho Y, Ofomaja AE (2006) Biosorption thermodynamics of cadmium on coconut copra meal as biosorbent. Biochem Eng J 30:117–123
Horsfall M, Spiff AI, Abia AA (2004) studies on the influence of mercaptoacetic acid(MAA) waste biomass on the adsorption of Cu2+ and Cd2+ from aqueous solution. Bull Korean Chem Soc 29:969–976
Hossain MA, Ngo NN, Guo WS, Setiadi GT (2012) Adsorption and desorption of copper(II) ions onto garden grass. Bioresour Technol 121:386–395
Hossain MA, Ngo HH, Guo WS, Nguyan TV, Vigneswaran S (2014) Performance of cabbage and cauliflower wastes for heavy metal removal. Desali Water Treat 52(1–2):844–860
Huang K, Zhu H (2013) Removal of Pb2+ from aqueous solution by adsorption on chemically modified muskmelon peel. Environ Sci Pollut Res 20:4424–4434
Huber GW, Iborra S, Corma A (2006) Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. Chem Rev 106:4044–4098
Iqbal M, Saeed A, Zafar SI (2009a) FTIR spectrophotometry, kinetics and adsorption isotherms modeling, ion exchange, and EDX analysis for understanding the mechanism of Cd2+ and Pb2+ removal by mango peel waste. J Hazard Mater 164:161–171
Iqbal M, Saeed A, Kalim I (2009b) Characterization of adsorptive capacity and investigation of mechanism of Cu2+, Ni2+ and Zn2+ adsorption on mango peel waste from constituted metal solution and genuine electroplating effluent. Sep Sci Technol 44:3770–3791
Ismaiel AA, Aroua MK, Yusoff R (2013) Palm shell activated carbon impregnated with task-specific ionic-liquids as a novel adsorbent for the removal of mercury from contaminated water. Chem Eng J 225:306–314
Jain M, Garg VK, Kadirvelu K (2013) Cadmium(II) sorption and desorption in a fixed bed column using sunflower waste carbon calcium-alginate beads. Bioresour Technol 129:242–248
Jalali M, Aboulghazi F (2013) Sunflower stalk, an agricultural waste, as an adsorbent for the removal of lead and cadmium from aqueous solutions. J Mater Cycles Waste Manag 15:548–555
Janaki V, Kamala-Kannan S, Shanthi K (2015) Significance of Indian peat moss for the removal of Ni(II) ions from aqueous solution. Environ Earth Sci 74(6):5351–5357
Jayaram K, Prasad MNV (2009) Removal of Pb(II) from aqueous solution by seed powder of Prosopis juliflora DC. J Hazard Mater 169:991–997
Kaczala F, Marques M, Hogland W (2009) Lead and vanadium removal from a real industrial wastewater by gravitational settling/sedimentation and sorption onto Pinus sylvestris sawdust. Bioresour Technol 100:235–243
Kang KC, Kim SS, Choi JW, Kwon SH (2008) Sorption of Cu2+ and Cd2+ onto acid and base-pretreated granular activated carbon and activated carbon fibre samples. J Ind Eng Chem 14:131–135
Kapur M, Mondal MK (2013) Mass transfer and related phenomena for Cr(VI) adsorption from aqueous solutions onto Mangifera indica sawdust. Chem Eng J 218:138–146
Karthikeyan KG, Elliott HA, Cannon FS (1996) Enhanced metal removal from wastewater by coagulant addition. In: Proceedings of 50th Purdue Industrial Waste Conference 50:259-267
Kataki R, Konwer D (2001) Fuelwood characteristics of some indigenous woody species of north-east India. Biomass Bioenergy 20:17–23
Kelly-Vargas K, Cerro-lopez M, Reyna-Tellez S, Bandala ER, Sanchez-Sales JL (2012) Biosorption of heavy metals in polluted water using different waste fruit cortex. Phys Chem Earth Parts A B C 37–39:26–29
Keng P-S, Lee S-L, Ha S-T, Hung Y-T, Ong S-T (2013) Cheap material to clean heavy metal polluted waters, In: Lichtfouse E et al. (eds) Green materials for energy, Products and Depollution, Environmental Chemistry for a Sustainable World 3, Springer Science+Business Media Dardrecht, pp 339–351
Khan NA, Ali SI, Ayub S (2001) Effect of pH on the removal of chromium (Cr) (VI) by sugar cane baggase. Sep Sci Technol 6:13–19
Khan MA, Ngabura M, Choong TSY, Masood H, Chuah LA (2012) Biosorption and adsorption of nickel on oil cake: batch and column studies. Bioresour Technol 13(1):35–42
Kim DH, Shin MC, Choi HD, Cl Seo, Baek K (2008) Removal mechanism of copper using steel making slag: adsorption and precipitation. Desalination 223(1–3):283–289
Kohler SJ, Cubillas P, Rodriguez-Blanco JD, Bauer C, Prieto M (2007) Removal of cadmium from wastewaters by aragonite shells and the influence of other divalent cations. Environ Sci Technol 41:112–118
Kongsuwan A, Patnukao P, Pavasant P (2009) Binary component sorption of Cu(II) and Pb(II) with activated carbon from Eucalyptus camaldulensis Dehn bark. J Ind Eng Chem 15:465–470
Kononova ON, Kholmogorov AG, Kachin SV, Mytykh OV, Konovova YS, Kalyakina OP, Pashkov GL (2000) Ion exchange recovery of nickel from manganese nitrate solutions. Hydrometallurgy 54:107–115
Konstantinou M, Kolokassidou K, Pashalidis I (2007) Sorption of Cu(II) and Eu(II) ions from aqueous solution by oliove cake. Adsorption 13:33–40
Koroki M, Saito S, Hashimoto H, Yamada T, Aoyoma M (2010) Removal of Cr(VI) from aqueous solutions by the clum of bamboo grass treated with concentrated sulfuric acid. Environ Chem Lett 8:197-207
Kristensen O (1996) Combined heat and power production based on gasification of straw and woodchips. In: Chartier P, Ferrero GL, Henius UM, Hultberg S, Sachau J, Wiinblad M (eds) Proceedings of the 9th European bioenergy conference, 1996, Copenhagen, vol 1. Pergamon, Elsevier Science Ltd., Oxford, pp 272–277
Kryvoruchko A, Yurlova AL, Karnilovich B (2002) Purification of water containing heavy metals by chelating-enhanced ultrafilteration. Desalination 144:243–248
Ku Y, Jung IL (2001) Photocatalytic reduction of Cr(VI) in aqueous solutions by UV irradiation with the presence of titanium dioxide. Water Res 35:135–142
Kumar PS, Ramalingam S, Kirupha SD, Murugesan A, Vidyadevii T, Sivanesan S (2011) Adsorption behaviour of nickel(II) onto cashew nut shell: equilibrium, thermodynamic, mechanism and process design. Chem Eng J 167:122–131
Kumar PS, Ramalingam S, Sathyaselvabala V, Kirupha SD, Murugesa A, Sivanesan S (2012a) Removal of cadmium(II) from aqueous solution by agricultural waste cashew nut shell. Korean J Chem Eng 29(6):756–768
Kumar PS, Gayathri R, Senthamarai C, Priyadharshini M, Fernando PSA, Srinath R, Kumar VV (2012b) Kinetics, mechanism, isotherm and thermodynamic analysis of adsorption of cadmium ions by surface-modified Strychnos potatorum seeds. Korean J Chem Eng 29(12):1752–1760
Landaburu-Aguirre J, García V, Pongrácz E, Keiski RL (2009) The removal of zinc from synthetic wastewaters by micellar-enhanced ultrafiltration: statistical design of experiments. Desalination 240:262–269
Landaburu-Aguirre J, Pongracz E, Sarpola A (2012) Simultaneous removal of heavy metals from phosphorous rich real wastewater by micellar-enhanced ultrafiltration. Sep Purif Technol 88:130–137
Lasheen MR, Ammar NS, Ibrahim HS (2012) Adsorption/desorption of Cd(II), Cu(II) and Pb(II) using chemically modified orange peel: equilibrium and kinetic studies. Solid State Sci 14(2):202–210
Lee SJ, Park JH, Ahn YT, Chung JW (2015) Comparison of heavy metal adsorption by peat moss and peat moss-derived biochar produced under different carbonization conditions. Water Air Soil Pollut 226:9
Leyva-Ramos R, Bernal-Jacome LA, Acosta-Rodriguez I (2005) Adsorption of cadmium (II) from aqueous solution on natural and oxidized corncob. Sep Purif Technol 45:41–49
Li MS, Fan YM, Xu F, Sun RC, Zhang XL (2010) Cold sodium hydroxide/urea based pretreatment of bamboo for bioethanol production: characterization of the cellulose rich fraction. Ind Crops Prod 32:551–559
Liu ZR, Zhou LM, Wei P, Zeng K, Wen CX, Lan HH (2008) Competitive adsorption of heavy metal ions on peat. J China Univ Min Technol 18:255–260
Liu ZR, Chen XS, Zhou LM, Peng WEI (2009) Development of a first-order kinetic based model for the adsorption of nickel onto peel. Mining Sci Technol (China) 19(2):230–243
López FA, Centeno TA, García-Díaz I, Alguacil FJ (2013) Texture and fuel characteristics of the char produced by the pyrolysis of waste wood, and the properties of activated carbons prepared from them. J Anal Appl Pyrolysis 104:551–558
Low KS, Lee CK, Leo AC (1995) Removal of metals from electroplating wastes using banana pith. Bioresour Technol 51:227–231
Lu AH, Zhong SJ, Chen J, Shi JX, Tang JL, Lu XY (2006) Removal of Cr(VI) and Cr(III) from aqueous solutions and industrial wastewaters by natural clinopyrrhotite. Environ Sci Technol 40:3064–3069
Lundh M, Jönsson L, Dahlquist J (2000) Experimental studies of the fluid dynamics in the separation zone in dissolved air flotation. Water Res 34:21–30
Mahvi AH, Maleki A, Eslami A (2004) Potential of rice husk and rice husk ash for phenol removal in aqueous systems. Am J Appl Sci 1(4):321–326
Malathi S, Krishnaveni N, Sudha R (2015) Adsorptive removal of lead(II) from an aqueous solution by chemically modified cottonseed cake. Res Chem Intermed. doi:10.1007/s11164-015-2149-4
Malkoc E, Nuhoglu Y (2005) Investigation of Ni II removal from aqueous solutions using tea factory waste. J Hazard Mater B127:120–128
Maranon E, Sastre H (1991) Heavy metal removal in packed beds using apple wastes. Bioresour Technol 38:39–43
Maranon E, Swarez F, Alonso F, Fernandez Y, Sastre H (1999) Preliminary study of iron removal from hydrochloric pickling liquor by iron exchange. Ind Eng Chem Res 38:2782–2786
Márquez-Reyes JM, López-Chuken UJ, Valdez-González A, Luna-Olvera HA (2013) Removal of chromium and lead by a sulfate-reducing consortium using peat moss as carbon source. Bioresour Technol 144:128–134
Marshall WE, Champagne ET, Evans WJ (1993) Use of rice milling byproducts (hulls and bran) to remove metal ions from aqueous solution. J Environ Sci Health A 28:1977–1992
Martins AE, Pereira MS, Jorgetto AO, Martines MAU, Silva RIV, Saekia MJ, Castro GR (2013) The reactive surface of Castor leaf [Ricinus communis L.] powder as a green adsorbent for the removal of heavy metals from natural river water. Appl Surf Sci 276:24–30
McKendry P (2002) Energy production from biomass (part 1): overview of biomass. Bioresour Technol 83:37–46
Memon JR, Memon SQ, Bhanger MI, Memon GZ, El-Turki A, Allen GC (2008) Characterization of banana peel by scanning electron microscopy and FT-IR spectroscopy and its use for cadmium removal. Colloids Surf B Biointerfaces 66:260–265
Memon JR, Memon SQ, Bhanger MI, El-Turki A, Keith R, Hallam Allen GC (2009) Banana peel: a green and economical sorbent for the selective removal of Cr(VI) from industrial wastewater. Colloids Surf B Biointerfaces 70:232–237
Mendez A, Barriya S, Fidalgo JM, Gasco G (2009) Adsorbent material from paper industry waste materials and their use in Cu(II) removal from water. J Hazard Mater 165(1–3):736–743
Meneghel AP, Goncalves AC Jr, Strey L, Rubio T, Schwantes D, Casarin J (2013) Biosorption and removal of chromium from water by using moringa seed cake (Moringa oleifera Lam.). Quim Nova 36(8):104–110
Mirbagherp SA, Hosseini SN (2004) Pilot plant investigation on petrochemical wastewater treatment for the removal of copper and chromium with the objective of reuse. Desalination 171:85–93
Mishra SP, Dubey SS, Tiwari D (2004) Rapid and efficient removal of Hg(II) by hydrous manganese and tin oxides. J Colloid Interface Sci 279:61–67
Mohammad AW, Othman R, Hilal N (2004) Potential use of nanofiltration membranes in treatment of industrial wastewater from Ni-P electroless plating. Desalination 168:241–252
Mohammad AAG, Juiki L, Yousel S, Nasir AL, Gavin W, Mohammad NMA (2010) Adsorption mechanism of remaining heavy metals and dyes from aqueous solution using date pits solid adsorbent. J Hazard Mater 185:401–407
Mohammadi T, Moheb A, Sadrzadeh M, Razmi A (2005) Modelling of metal ion removal from wastewater by electrodialysis. Sep Purif Technol 41:73–82
Mohammadi SZ, Karimi MA, Afzali D, Mansouri F (2010) Removal of Pb(II) from aqueous solutions using activated carbon from sea-buckthorm stones by chemical activation. Desalination 262(1–3):86–93
Mohammod M, Sen TK, Maitra S, Dutta BK (2011) Removal of Zn2+ from aqueous solution using castor seed hull. Water Air Soil Pollut 215:609–620
Mohan D, Singh KP (2002) Single- and multi-component adsorption of cadmium and zinc using activated carbon derived from bagasse—an agricultural waste. Water Res 36:2304–2318
Mohan S, Sreelakshmi G (2008) Fixed bed column study for heavy metal removal using phosphate treated rice husk. J Hazard Mater 153:75–82
Mohsen-Nia M, Montazeri P, Modaress H (2007) Removal of Cu2+ and Ni2+ from wastewater with a chelating agent and reverse osmosis processes. Desalination 217:276–281
Molinari R, Poerio T, Argurio P (2008) Selevtive separation of copper (II) and nickel (II) from aqueous media using the complexation-utrafiltration process. Chemosphere 70(3):341–348
Mondal MK (2010) Removal of Pb(II) from aqueous solution by adsorption/desorption modified orange peel: Equilibrium and kinetic studies. Solid State Sci 14:202–210
Mondal MK (2012) Removal of Pb(II) from aqueous solution by adsorption using activated tea waste. Korean J Chem Eng 27(1):144–151
Mondal DK, Nandi BK, Purkait MK (2013) Removal of mercury (II) from aqueous solution using bamboo leaf powder: equilibrium, thermodynamic and kinetic studies. J Environ Chem Eng 1:891–898
Monteagudo JM, Ortiz MJ (2000) Removal of inorganic mercury from mine wastewater by ion exchange. J Chem Tech Biotechnol 75:767–772
Munagapati VS, Yarramuthi V, Nadavala SK, Alla SR, Abburi K (2010) Biosorption of Cu(II), Cd(II) and Pb(II) by Acacia leucocephala bark powder: kinetics, equilibrium and thermodynamics. Chem Eng J 157:357–365
Murthy ZVP, Chaudhari LB (2008) Application of nanofiltration for the rejection of nickel ions from aqueous solutions and estimation of membrane transport parameters. J Hazard Mater 160:70–77
Muthukrishnan M, Guha BK (2008) Effect of pH on rejection of hexavalent chromium by nanofiltration. Desalination 219:171–178
Nadaroglu H, Kalkan E, Demir N (2010) Removal of copper from aqueous solution using red mud. Desalination 251:90–95
Nagah WSW, Hanafiah MAKM (2008) Removal of heavy metal ions from wastewater by chemically modified plant wastes as adsorbents: a review. Bioresour Technol 99:3935–3948
Nagashanmugam KB, Srinivasan K (2010) Evaluation of carbon derived fror Gingelly oil cake for the removal of lead(II) from aqueous solutions. J Environ Sci Eng 52(4):349–360
Naik S, Goud VV, Rout PK, Jacobson K, Dalai AK (2010) Characterization of Canadian biomass for alternative renewable biofuel. Renew Energy 35:1624–1631
Naiya TK, Bhattacharya AK, Mandal S, Das SK (2009) The sorption of lead (II) ions on rice husk ash. J Hazard Mater 163:1254–1264
Nakbanpote W, Thiravetyan P, Kalambaheti C (2000) Preconcentration of gold by rice husk ash. Miner Eng 13:391–400
Namasivayam C, Periasamy K (1993) Bicarbonate-treated peanut hull carbon for mercury(II) removal from aqueous solutions. Water Res 27:1663–1668
Nanseu-Njiki CP, Tchamango SR, Ngom PC, Darchen A, Ngameni E (2009) Mercury(II) removal from water by electrocoagulation using aluminium and iron electrodes. J Hazard Mater 168:1430–1436
Nataraj SK, Hosamani KM, Aminabhavi TM (2007) Potential application of an electrodialysis pilot plant containing ion-exchange membranes in chromium removal. Desalination 217:181–190
Nguyen CM, Bang S, Cho J, Kim KW (2009) Performance and mechanism of arsenic removal from water by a nanofiltration membrane. Desalination 245:82–94
Okoye AI, Ejikeme PM, Onukwuli OD (2010) Lead removal from wastewater using fluted pumpkin seed hull activated carbon: adsorption modelling and kinetics. Int J Environ Sci Tech 7(4):793–800
Olguin MT, Lopez-Gonzalez H, Serrano-Gomez J (2013) Hexavalent chromium removal from aqueous solutions by Fe-modified peanut husk. Water Air Soil Pollut 224:1654
Oliveira FD, Paula J, Freitas OM, Figueiredo SA (2009) Copper and lead removal by peanut hulls: equilibrium and kinetic studies. Desalination 248:931–940
Onal Y, Akmil-Bas C, Sarıcı-Ozdemir C, Erdogan S (2007) Textural development of sugar beet bagasse activated with ZnCl2. J Hazard Mater 142:138–143
Ouensanga A, Largitte L, Arsene MA (2003) The dependence of char yield on the amounts of components in precursors for pyrolysed tropical fruit stones and seeds. Micropor Mesopor Mater 59:85–91
Ozer A, Ozer D (2004) The adsorption of copper(II) ions on to dehydrated wheat bran (DWB): determination of the equilibrium and thermodynamic parameters. Proc Biochem 39:2183–2191
Pagano M, Petruzzelli D, Tiravanti D, Passino R (2000) Pb/Fe separation and recovery from automobile battery wastewater by selective ion exchange. Solvent Extr Ion Exch 18:387–399
Pandey R, Prasad RL, Ansari NG, Murthy RC (2015) Utilization of NaOH modified Desmostachya bipinnata (kush grass) leaves and Bambusa aradinacea (bamboo) leaves for Cd(II) removal from aqueous solution. J Environ Chem Eng 3(1):593–602
Parab H, Joshi S, Shenoy N, Lali A, Sharma US, Sudersanan M (2006) Determination of kinetic and equilibrium parameters of the batch adsorption of Co(II), Cr(III) and Ni(II) onto coir pith. Process Biochem 41:609–615
Park HG, Kim TW, Chae MY, Yoo IK (2007) Activated carbon-containing alginate adsorbent for the simultaneous removal of heavy metals and toxic organics. Process Biochem 42:1371–1377
Pehlivan E, Altun T (2008) Bioadsorption of chromium(VI) ion from aqueous solutions using walnut, hazelnut and almond shell. J Hazard Mater 155:378–384
Pehlivan E, Altun T, Cetin S, Bhanger MI (2009a) Lead sorption by waste biomass of hazelnut and almond shell. J Hazard Mater 167:1203–2128
Pehlivan E, Altun T, Parlayici S (2009b) Utilization of barley straws as biosorbents for Cu2+ and Pb2+ ions. J Hazard Mater 164:982–986
Pehlivan E, Altun T, Cetin S, Bhangerb MI (2009c) Lead sorption by waste biomass of hazelnut and almond shell. J Hazard Mater 167:1203–1208
Pettersson A, Amand L-E, Steenari B-M (2008) Leaching of ashes from co-combustion of sewage sludge and wood—part I: recovery of phosphorus. Biomass Bioenergy 32:224–235
Polat H, Erdogan D (2007) Heavy metal removal from wastewater by ion flotation. J Hazard Mater 148:267–273
Prasad S, Singh A, Joshi HC (2007) Ethanol as an alternative fuel from agricultural, industrial and urban residues. Resour Conserv Recycl 50:1–39
Rafatullah M, Sulaiman O, Hashim R, Ahmad A (2012) Removal of cadmium (II) from aqueous solutions by adsorption using meranti wood. Wood Sci Technol 46:221–241
Rao M, Parwate AV, Bhole AG (2002) Removal of Cr(VI) and Ni(II) from aqueous solution using bagasse and fly ash. Waste Manage 22:821–830
Rashed MN (2006) Fruit stones from industrial waste for the removal of lead ions from polluted water. Environ Monit Assess 119:31–41
Raveendran K, Ganesh A, Khilar K (1995) Influence of mineral matter on biomass pyrolysis characteristics. Fuel 74:1812–1822
Reddy N, Yang Y (2005) Biofibers from agricultural byproducts for industrial applications. Trends Biotechnol 23(1):22–27
Reddy DHK, Seshaiaha K, Reddy AVR, Raoc MM, Wang MC (2010) Biosorption of Pb2+ from aqueous solutions by Moringa oleifera bark: equilibrium and kinetic studies. J Hazard Mater 174:831–838
Reddy DHK, Ramana DKV, Seshaiah Reddy AVR (2011) Biosorption of Ni(II) from aqueous phase by Moringa oleifera bark, a low cost biosorbent. Desalination 268:150–157
Reyes I, Villarroel M, Diez MC, Navia R (2009) Using lignimerin (a recovered organic material from Kraft cellulose mill wastewater) as sorbent for Cu and Zn retention from aqueous solutions. Bioresour Technol 100:4676–4682
Sabry R, Hafez A, Khedr M, El-Hussanin A (2007) Removal of lead by an emulsion liquid membrane: part I. Desalination 212:165–175
Sadrzadeh M, Mohammadi T, Ivakpour J, Kasiri N (2008) Seperation of lead ions from wastewater using electrodialysis: comparing mathematical and neural network modelling. Chem Eng J 144:431–441
Sadrzadeha M, Mohammadi T, Ivakpour J, Kasiri N (2009) Neural network modelling of Pb2+ removal from wastewater using electrodialysis. Chem Eng Process 48:1371–1381
Saeed A, Iqbal M, Akhtar W (2005) Removal and recovery of lead(II) from single and multimetal (Cd, Cu, Ni, Zn) solutions by crop milling waste (black gram husk). J Hazard Mater 11:65–73
Saha R, Mukherjee K, Saha I, Ghosh A, Ghosh SK, Saha B (2013) Removal of hexavalent chromium from water by adsorption on mosambi (Citrus limetta) peel. Res Chem Intermed 39:2245–2257
Sahu MK, Mandal S, Dash SS, Badhai P, Patel RK (2013) Removal of Pb(II) from aqueous solution by acid activated red mud. J Environ Chem Eng 1(4):1315–1324
Sampera E, Rodrígueza M, De la Rubia MA, Prats D (2009) Removal of metal ions at low concentration by micellar-enhanced ultrafiltration (MEUF) using sodium dodecyl sulfate (SDS) and linear alkylbenzene sulfonate (LAS). Sep Purif Technol 65:337–342
Sander B (1997) Properties of Danish biofuels and the requirements for power production. Biomass Bioenergy 12:177–183
Sarin V, Pant KK (2006) Removal of chromium from industrial waste by using eucalyptus bark. Bioresour Technol 97(1):15–20
Sassi M, Bestani B, Said AH, Benderdouche N, Guibal E (2010) Removal of heavy metal ions from aqueous solution by a local dairy sludges as a biosorbent. Desalination 262:243–250
Scatchard G (1949) The attractions of proteins for small molecules and ions. Ann Acad Sci N Y 51:600–672
Schiewer S, Patil SB (2008) Modeling the effect of pH on biosorption of heavy metals by citrus peels. J Hazard Mater 157:8–17
Scurlock JMO, Dayton DC, Hames BB (2000) An overlooked biomass resource? Biomass Bioenergy 19:229–244
Semerjian L, Ayoub GM (2003) High-pH-magnesium coagulation–flocculation in wastewater treatment. Adv Environ Res 7:389–403
Şensöz S, Demiral İ, Gercel HF (2006) Olive bagasse (Olea europea L.) pyrolysis. Bioresour Technol 97(3):429–436
Shafique U, Ijaz A, Salman M, Zaman W, Jamil N, Rehman R, Javaid A (2012) Removal of arsenic from water using pine leaves. J Taiwan Inst Chem Eng 43:256–263
Shahalam AM, Al-Harthy A, Al-Zawhry A (2002) Feed water pretreatment in RO systems in the Middle East. Desalination 150:235–245
Shammas NK (2004) Coagulation and flocculation. In: Wang LK, Hung YT, Shammas NK (eds) Physicochemical treatment processes, vol 3. Humana Press, New Jersey, pp 103–140
Shen DK, Gu S, Luo KH, Bridgwater AV, Fang MX (2009) Kinetic study on thermal decomposition of woods in oxidative environment. Fuel 88:1024–1030
Sheng GD, Wang SW, Hua J, Lu Y, Li JX, Dong YH, Wang XK (2009) Adsorption of Pb(II) on diatomite as affected via aqueous solution chemistry and temperature. Colloid Surf 339:159–166
Shukla SR, Pai RS (2005) Adsorption of Cu(II), Ni(II) and Zn(II) on modified jute fibres. Bioresour Technol 96:1430–1438
Shukla SR, Pai RS, Shendarkar AD (2006) Adsorption of Ni(II), Zn(II) and Fe(II) on modified coir fibres. Sep Purif Technol 47:141–147
Sobhanardakani S, Parvizimosaed H, Olyaie E (2013) Heavy metals removal from wastewaters using organic solid waste—rice husk. Environ Sci Pollut Res 20:5265–5271
Soliman EM, Ahmad SA, Fadl AA (2011) Reactivity of sugarcane bagasse as a natural solid phase extractor for selective removal of Fe(III) and heavy metal ions from natural water samples. Arab J Chem 4:63–70
Song S, Lopez-Valdivieso A, Hernandez-Campos DJ, Peng C, Monroy-Fernandez MG, Razo-Soto I (2006) Arsenic removal from high-arsenic water by enhanced coagulation with ferric ions and coarse calcite. Wat Res 40:364–372
Stniannopkao S, Sreesai S (2009) Utilization of pulp and paper industrial waste to remove heavy metal from metal finishing wastewater. J Environ Manag 90(11):3283–3289
Sud D, Mahajan G, Kaur MP (2008) Agricultural waste materials as potential adsorbent for sequestering heavy metal ions from aqueous solutions- a review. Bioresour Technol 99:6017–6027
Sun G, Shi W (1998) Sunflower stalks as adsorbents for the removal of metal ions from wastewater. Ind Eng Chem Res 37:1324–1328
Sun G, Xu X (1997) Sunflower stalks as adsorbents for color removal from textile wastewater. Ind Eng Chem Res 36:808–812
Szpyrkowicz L, Juzzolino C, Kaul SN (2001) A comparative study on oxidation of disperse dyes by electrochemical process, ozone, hypochlorite and fenton reagent. Water Res 35(9):2129–2136
Tamaki Y, Mazza G (2010) Measurement of structural carbohydrates, lignins, and micro-components of straw and shives: effects of extractives, particle size and crop species. Ind Crop Prod 31:534–541
Tan WT, Ooi ST, Lee CK (1993) Removal of chromium (VI) from solution by coconut husk and palm pressed fibres. Environ Technol 14:277–282
Taner F, Ardic I, Halisdemir B, Pehlivan E (2004) Biomass use and potential in Turkey. In: Biomass and agricultural: sustainability, markets and policies. OED publication
Tassel F, Rubio J, Misra M, Jena BC (1997) Removal of mercury from gold cyanide solution by dissolved air flotation. Miner Eng 10:803–811
Tazrouti N, Amrani M (2009) Chromium(VI) adsorption onto activated kraft lignin produced from alfa grass (Stipa tinacissima). Bio Resour 4(2):740–755
Tessele F, Misra M, Rubio J (1998) Removal of Hg, As and Se ions from gold cyanide leach solutions by dissolved air flotation. Miner Eng 11:535–543
Tillman DA, Harding NS (2004) Fuels of opportunity: characteristics and uses in combustion systems. Elsevier B.V, Amsterdam, p 312
Tofan L, Teodosiu C, Paduraru C, Wenkert R (2013) Cobalt (II) removal from aqueous solutions by natural hemp fibers: batch and fixed-bed column studies. Appl Surf Sci. doi:10.1016/j.apsusc.2013.06.151
Trevino-Corderoa H, Juárez-Aguilara LG, Mendoza-Castilloa DI, Hernández-Montoyaa V, Bonilla-Petriciolet A, Montes-Moranb MA (2013) Synthesis and adsorption properties of activated carbons from biomass of Prunus domestica and Jacaranda mimosifolia for the removal of heavy metals and dyes from water. Ind Crops Prod 42:315–323
Vaughan T, Seo CW, Marshall WE (2001) Removal of selected metal ions from aqueous solution using modified corncobs. Bioresour Technol 78:133–139
Vlyssides AG, Israilides CJ (1997) Detoxification of tannery waste liquors with an electrolysis system. Env Pollut 97:147–152
Wartelle LH, Marshall WE (2006) Quaternized agricultural by-products as anion exchange resins. J Environ Manage 78:157–162
WASDE Report (2013) World wheat supply and use 524:18–19
Waters A (1990) Dissolved air flotation used as primary separation for heavy metal removal. Filtrat Sep 27(2):70–73
Williams PT, Reed AR (2006) Development of activated carbon pore structure via physical and chemical activation of biomass fibre waste. Biomass Bioenergy 30:144–152
Wong KK, Lee CC, Low KS, Haron MJ (2003) Removal of Cu and Pb by tartaric acid modified rice husk from aqueous solutions. Chemosphere 50:23–28
Yanik J, Ebale S, Kruse A, Saglam M, Yuksel M (2007) Biomass gasification in supercritical water: part 1, effect of the nature of biomass. Fuel 86:2410–2415
Yu HW, Samani Z, Hanson A, Smith G (2002) Energy recovery from grass using two-phase anaerobic digestion. Waste Manag 22:1–5
Yu JX, Wang LY, Chi RA, Zhang YF, Xu ZG, Guo J (2013) Adsorption of Pb2+, Cd2+ and Zn2+ from aqueous solution by modified sugarcane bagasse. Res Chem Intermed 41:1525–1541
Yurlova L, Kryvoruchko A, Kornilovich B (2002) Removal of Ni(II) ions from wastewater by miceller-enhanced ultrafilteration. Desalination 144:255–260
Zabel T (1984) Flotation in water treatment. In: Ives KJ (ed) The scientific basis of flotation. Martinus Nijhoff Publishers, The Hague, pp 349–378
Zamboulis D, Peleka EN, Lazaridis NK, Matis KA (2011) Metal ion separation and recovery from environmental sources using various flotation and sorption techniques. J Chem Technol Biotechnol 86:335–344
Zheng L, Danga Z, Yia X, Zhanga H (2010) Equilibrium and kinetic studies of adsorption of Cd(II) from aqueous solution using modified corn stalk. J Hazard Mater 176:650–656
Zheng L, Zhu C, Dang Z, Zhang H, Yi X, Liu C (2012) Preparation of cellulose derived from corn stalk and its application for cadmium ion adsorption from aqueous solution. Carbohydr Polym 90:1008–1015
Zhu CS, Waref LP, Chen W (2009) Removal of Cu(II) from aqueous solution by agricultural by products-peanut hull. J Hazard Mater 186:739–746
Zuo XJ, Balasurbramanian R, Fu DF, Li H (2012) Biosorption of copper, zinc and cadmium using sodium hydroxide immersed Cymbopogon schoenanthus L. Spreng (Lemon grass). Ecol Eng 49:186–189
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
About this article
Cite this article
Malik, D.S., Jain, C.K. & Yadav, A.K. Removal of heavy metals from emerging cellulosic low-cost adsorbents: a review. Appl Water Sci 7, 2113–2136 (2017). https://doi.org/10.1007/s13201-016-0401-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13201-016-0401-8