Marine algae used in bioadsorption removal of heavy and lanthanide metals.
\r\n\tHydrogen gas is the key energy source for hydrogen-based society. Ozone dissolved water is expected as the sterilization and cleaning agent that can comply with the new law enacted by the US Food and Drug Administration (FDA). The law “FDA Food Safety Modernization Act” requires sterilization and washing of foods to prevent food poisoning and has a strict provision that vegetables, meat, and fish must be washed with non-chlorine cleaning agents to make E. coli adhering to food down to “zero”. If ozone dissolved water could be successively applied in this field, electrochemistry would make a significant contribution to society.
\r\n\r\n\t
\r\n\tOxygen-enriched water is said to promote the growth of farmed fish. Hydrogen dissolved water is said to be able to efficiently remove minute dust on the silicon wafer when used in combination with ultrasonic irradiation.
\r\n\tAt present researches on direct water electrolysis have shown significant progress. For example, boron-doped diamonds and complex metal oxides are widely used as an electrode, and the interposing polymer electrolyte membrane (PEM) between electrodes has become one of the major processes of water electrolysis.
\r\n\t
\r\n\tThe purpose of this book is to show the latest water electrolysis technology and the future of society applying it.
Glaucoma is a group of diseases that affect the optic disc, causing a specific type of optic neuropathy characterized by specific changes in the optic disc and visual field that eventually may progress to blindness. A feature common to most of the glaucoma types is high intraocular pressure, which to date is virtually the only target for treatment. The aim of the treatment is to decrease the intraocular pressure to a target pressure that is specific for each patient. This specific pressure is supposed to prevent further deterioration in visual field and irreversible blindness. Unfortunately, despite achieving a target pressure, there is a subpopulation of glaucoma patients who still progress gradually to blindness. This chapter will discuss possible reasons for this phenomenon in those patients who achieve the target pressure.
The World Health Organization (WHO) estimated that in 2014, 285 million people (4%) out of the 7.2 billion world population had either low vision (246 million) or blindness (49 million) [1]. Ninety percent of these live in low-economic settings and 82% are aged over 50 years. Eighty percent of visual impairment can be prevented or cured. The best examples are correction of refractive errors and cataract surgery.
The most common cause for blindness worldwide is cataract (47%), and it is reversible upon surgery. The second common cause for blindness is glaucoma (12%), and it is the most common cause for irreversible blindness. This is followed by age-related macular degenera-tion (5%).
Glaucoma is a distinctive group of optic nerve neuropathies characterized by specific optic disc and visual field changes, usually with an increase in intraocular pressure (IOP). In the past, a true IOP of up to 21 mmHg was considered normal in healthy individuals. Today, some consider an IOP between 18 and 22 as borderline. The term “true IOP” addresses the corrected IOP according to the thickness of the cornea and other parameters that influence the IOP. The main optic disc change is the increase of the cup (cupping) and decrease of the rim that contains the axons from the retinal ganglion layer (Figure 1). Early signs for this include disc notching, increased excavation, retinal nerve fiber defects, and papillary flame-shape hemorrhages. The early changes in visual field include Bjerrum defects (scotomata), paracentral scotoma, nasal step, and arcuate scotoma. As the disease progresses, visual field defects increase, first in depth and then in size. Arcuate scotoma may join nasal field, and when these increase toward the center and the periphery, tunnel vision and/or a temporal crescent or a few visual islands remains. Eventually, these disappear too and the patient remains with no light perception. The changes in visual field correspond and follow closely with the changes in the optic disc. The chronic forms of this group are asymptomatic until advanced and irreversible visual loss occurs. Patients preserve normal visual acuity (even of 20/20) in one or both eyes until late in the disease. Such patients may not be aware of the small defects early in the course of the disease or even advanced concentric visual loss and tunnel vision, until they completely lose their vision in one or both eyes.
An advanced stage of glaucomatous optic disc damage showing thinning of the rim. The cup/disc ratio is almost 1 (subtotal excavation).
Two theories explain the neuronal loss in glaucoma. The first claims that mechanical force exerted on the optic disc causes direct destruction. The second claims that compromised blood flow causes damage. The damage may be caused also by a combination of these two processes. The end point is apoptosis of the ganglion cell layer.
The visual field loss (scotoma) in glaucoma has a distinctive pattern that differs from visual loss due to other causes (Figures 2 and 3). The visual field defects include Bjerrum scotoma, paracentral scotoma, nasal step, and arcuate defect. These defects correspond to retinal nerve fiber loss, which usually begins in the arcuate bundles and the nasal fibers and ends with the papillomacular bundle.
Advanced visual field loss of the right eye in a glaucoma patient. On the left, a 24-2 Humphrey visual field demonstrating a concentric visual field loss with only a small para-central island remained. The fixation point is split. This is also demonstrated in the same patient on the right with a 10-2 visual field. Glaucoma surgery at this point can cause the loss of the fixation and a decrease in best-corrected visual acuity to counting fingers.
24-2 and 10-2 Humphrey visual fields of a patient with advanced field damage. The damage encroaches on the fixation but does not split it. In this case, successful trabeculectomy with mitomycin-C was performed. The visual field remained unchanged. The best-corrected visual acuity remained 20/60, and the intraocular pressure decreased from 28 to 34 mmHg to 10–12 mmHg and remained at this level.
When superior and inferior nasal steps coalescence with arcuate defects and spread centrally and peripherally, tunnel vision evolves. The visual acuity may remain intact (best-corrected visual acuity 20/20) in this situation. Eventually, central vision and/ or temporal peripheral island(s) may remain; when these are lost, the patient remains with no light perception. Occurrence in both eyes results in total blindness. In most types of glaucoma, the chronic ones, the patient may not be aware of the visual field loss, unless comparing each eye to the other. This is the reason that glaucoma is called the silent thief of vision. The patient may present only when the visual acuity in one eye is completely lost because the overlapping between the visual field of both eyes, micro-saccades, and most importantly, turning the head toward the area of interest. Therefore, screening of the population is the most crucial measure to detect glaucoma patients and treat them early.
The goal of treatment is to stabilize the visual field and prevent further deterioration in visual field and visual loss. Unfortunately, currently, the main treatment is aimed only at reducing the intraocular pressure (IOP) and achieving the ideal IOP (target IOP), which differs for each patient and is determined by the type of glaucoma, its severity, progression, patient compliance, and allergy to medications. In general, it should be as low as possible but not too low (hypotonia). Screening of the population includes observing the optic disc and checking the IOP. It should be performed at least every 5 years before the age of 40 years and every 6 months after the age of 40 years.
To date, visual loss in glaucoma is irreversible because of the death of ganglion cells and their axons. The treatment is aimed to prevent continuous visual field loss and is divided into medical, laser, and surgical methods. To prevent visual field loss, the intraocular pressure should be at or below the target IOP, which is individual to each patient and related to the type of glaucoma, severity of the disease, patient’s compliance, and allergy to medications. To date, there is no treatment addressing the different genetic defects and molecular mechanisms causing or related to glaucoma. The first line of treatment is usually medications. To enhance treatment, laser treatment may be applied. Some of the laser treatments such as selective laser trabeculoplasty have a short span of effectiveness, usually 1–1.5 years. If these fail, surgery is indicated. The number of medications, laser, and surgical procedures is wide and is determined mainly by the type of glaucoma.
Screening for glaucoma should include the entire population and should be composed of observation of the optic disc and documentation of the cup-disc ratio (C/D ratio) and other features of glaucomatous optic disc damage and intraocular pressure. Screening is usually performed every 5 years and over the age of 40 years twice a year. Patients with higher risk for glaucoma (e.g., family history of glaucoma, pseudoexfoliative syndrome, pigmentary dispersion syndrome, borderline IOP, etc.) may be routinely evaluated more often. Every patient who is diagnosed with glaucoma should be on appropriate medications permanently unless successful surgery has been performed, and even than the patient should be routinely followed.
The follow-up is every 3–4 months for lifetime including after successful surgery. If aggravation occurs, the follow-up intervals may be more frequent. Examination should be performed at different hours of the day, and a diurnal curve is indicated for patients with controlled IOP under medications and continuous visual field damage. The diurnal curve is performed every 4 hours and may even be increased to every 2 hours under medications. Some types of glaucoma such as pseudoexfoliative and pigmentary have a high fluctuation rate that may be missed by routine IOP examination. It is imperative to perform surgery in a timely manner, before the glaucoma is too advanced and before splitting of the fixation on visual field testing. Patients with complete splitting of the fixation are at higher risk to lose their central vision after surgery. Except for glaucoma surgery, other procedures may be required and may result in decrease of IOP. Cataract surgery in presence of risk factors such as hard nucleus (brown, red or black cataract), pseudoexfoliation, phakodonesis, lens subluxation, small pupil, ocular surface disorders such as ocular cicatricial pemphigoid, and Fuch’s corneal dystrophy should be performed early. As the number of risk factors increases, surgery should be performed earlier. Visual field should also be obtained for these patients before surgery, if the glaucoma is advanced (C/D ratio of 0.9 or more).
Patients at high risk to lose their vision are those who do not take their medications regularly and/or do not follow-up with their ophthalmologist at regular intervals as indicated above. Other major factors for visual loss are late diagnosis that may occur with all types of chronic glaucomas and slow decision making. Aggressive glaucoma and poor surgical outcomes may contribute to visual loss.
The aim of treatment at present is controlling the IOP to prevent further deterioration in visual fields. The loss of visual field is irreversible. The ideal IOP should be low enough to prevent visual field loss without compromising the functions of the eye. Each patient has a desirable range of IOP—target IOP, which varies between individuals and depends on the aggressiveness of the disease. The aggressiveness of the disease is determined by the IOP, its fluctuations, the type of glaucoma, and the damage to the optic disc and visual field. In normal tension glaucoma, the target IOP is usually less than in other types of glaucoma, because even with normal pressures, the damage continues to progress. The IOP is constantly changing. It depends on the hour (diurnal variations) and seasons. Most but not all subjects have the highest peak in IOP during the early morning.
To be considered as “controlled glaucoma,” the IOP should be within its target during the entire day in a long follow-up with constant use of anti-glaucoma medications or postoperatively. The patients should take their medications properly at a preset times and continuously. Thus, patients intolerant to anti-glaucoma medications or uncompliant are not considered controlled. The IOP may be assessed by diurnal curve every 4 hours, usually between 8 AM and 8 PM, because it changes constantly or even every 2 hours.
In this chapter, controlled glaucoma was defined as target IOP under diurnal curve of 4 hours in patients, who are dedicated in taking their anti-glaucoma medications or after surgery. It is a philosophic question whether patients who continue to lose their vision are controlled. Perhaps the definition should be patients who do not show further signs of deterioration. However, since the target pressure has been achieved, it is expected that the patients will demonstrate stability of their visual functions (i.e., visual fields), and this may not occur in a subset of these patients.
Secondary glaucomas such as pseudoexfoliative and pigmentary glaucomas have high fluctuations of IOP, which varies depending on the dispersion of pseudoexfoliation material or pigment in the anterior chamber angle. The IOP peaks are unpredictable and variable in time and amplitude and may be missed by diurnal curve even if performed every 2 hours. They may occur between the IOP measurements and may be missed. To overcome this, frequent IOP monitoring including at bedtime and at shorter intervals may reveal such patients. Patients with high and large fluctuations that are on full medical treatment may benefit from early glaucoma surgery, either trabeculectomy with mitomycin C or shunt procedure. Still, patients without IOP fluctuations may progress to blindness from other reasons as stated below.
People spend about one third of the day (6–8 hours) sleeping. The resting time may increase after retirement. The IOP increases at supine position compared with standing or sitting in healthy subjects by 2.47 ± 2.12 mmHg (mean ± standard deviation) (p < 0.001) when measured by non-contact tonometer Keeler, Pulsair EasyEye [2]. In another study, the IOP in sitting position was found to be 13.5 ± 2.0 mmHg in the right eye and 13.2 ± 2.3 mmHg in the left eye in healthy individuals [3]. The IOP increased in supine position to 16.8 ± 2.3 mmHg and 17.0 ± 2.3 mmHg, respectively (p = 0.001). This may result in deterioration of the optic disc and visual fields. Diurnal curve has probably no meaning if the patient is awakened at bedtime, and the pressure is measured while sitting.
The intracranial pressure (ICP) may also influence the progression of glaucoma [4, 5]. The ICP is directed through the subarachnoid space opposite to the IOP through the lamina cribrosa, and the difference between them is the translaminar pressure gradient. Theoretically, if this is low, the progression may be slower than if it is high but this may not be true. A high ICP and IOP with a low gradient may be sufficient to cause increased optic disc damage because of the increased shearing force in the lamina cribrosa and decrease in axonal plasma flow. This may initiate or facilitate axonal apoptosis.
Most ophthalmologists do not live with their glaucoma patients and have no idea about their behavior in daily life. The patients may sleep on their affected eye(s), and this causes further increase of the IOP in addition to the increase caused by supine position. When the eye leans against the bed or pillow or when the entire mass of the head is over all or part of the globe, IOP is increased by 33%. Thus, the physician should inquire about the sleeping habits of the glaucoma patients. Actually, increase in IOP measurement can be seen in patients who squeeze their eyes during evaluation with Goldmann tonometer, as well as with some other instruments. It can also be seen if the examiner presses the globe during IOP measurement.
Glaucoma patients are usually older and have many associated aging and pathologic conditions, including atherosclerosis and systemic hypertension. Other ischemic diseases such as diabetes mellitus may also be encountered. Taking antihypertensive drugs before sleeping increases the risk for anterior ischemic optic neuropathy (AION) [6]. Antihypertensive medications decrease the perfusion into the optic disc, and this may join atherosclerotic changes in the blood vessels. AION may be difficult to diagnose in patients with advanced glaucoma. In advanced glaucoma, the cup may be large (cup/disc ratio of 0.8 or more), and the rim is thin enough not to distinguish pallor of the rim following additional AION. In addition, AION field defects may be superimposed on the glaucoma visual field defects. In advanced glaucoma, the visual field scotomata may be large enough (e.g., tubular vision) to prevent detection of the additional scotomata caused by AION. According to the vascular theory, damage to the optic nerve may be caused also from ischemia if the optic disc does not receive enough oxygen even without AION. This damage is added to the damage caused by the mechanical effect of optic disc compression.
Patients with glaucoma suffer loss of axons of the ganglion cells as they pass the optic disc. Two theories explain the axonal loss. The first one is mechanical. According to this theory, the force caused by the IOP impedes axonal transport (flow) (micro-strangulation) and this may trigger axonal apoptosis [7]. The second theory is vascular. This means that the IOP impedes vascular supply to the optic disc. This causes a relative ischemia to the optic disc and triggers apoptosis. It is probable that both mechanisms coexist and the mechanical force may have a greater influence. Nonetheless, apoptosis, and not degeneration/necrosis, is the mechanism of axonal death in glaucoma. Apoptosis is programmed cell death, while necrosis is a different process involving extracellular components of inflammation. It consists of several pathways initiated be certain extracellular ligands such as programmed death ligand 1 (PD-L1), Fas ligand (FasL), tumor necrosis factor (TNF), nerve growth factor (NGF), growth factors, and others (Figure 4) [8, 9]. These molecules attach to receptors on the cell wall such as tropomyosin kinase receptor (TRK), tyrosine kinase receptor (RTK), receptor of apoptosis signal factor (Fas), and tissue necrosis factor receptor (TNFR) that trigger intracellular cascades that involve multiple pathways and molecules including the caspase cascade. These processes occur in the cytoplasm, endoplasmic reticulum, and mitochondria that lead signals to the nucleus to degenerate. The end result is shrinkage of the nucleus, fragmentation of the deoxyribonucleic acid (DNA), and death of the cell. It is possible that some additional mechanisms and pathways exist that involve adjacent cells such as astrocytes, oligodendrocytes, and even vascular endothelial cells. Despite controlled IOP, the apoptosis may continue once started causing additional ganglion cell death. Ganglion cells in different stages of apoptosis may “signal” adjacent normal cells to commence with apoptosis cascade, leading to further loss of neuronal cells.
The pathways of apoptosis. Interference with any of these steps may prevent the apoptosis cascade.
Patients with high IOP fluctuations are not controlled and may benefit from early surgery such as trabeculectomy with mitomycin C or shunt procedures. These patients can be traced because they usually have secondary glaucoma mainly pseudoexfoliative and pigmentary. It is worthwhile to ask the patients to sleep at 20–30° head-up position. The IOP decreases when the bed head is tilted up in 30° and is 14.2 ± 2.3 mmHg OD and 14.1 ± 1.9 OS and not when the patient is sleeping on multiple pillows (16.3 ± 2.4 OD and 16.5 ± 2.6 OS) [3]. In another study, the IOP decreased from 16.02 ± 1.65 to 14.5 ± 1.36 mmHg [10]. The IOP may decrease by 9.33% in glaucoma patients, and this effect is found in 82% of them. Patients should avoid sleeping on their affected eye(s). Sleeping over the back or even on the side as long as the orbital rim is lying against the pillow is the best option for these patients. Antihypertensive medications should be taken when the patient is awake and active, usually in the morning and not at bedtime. It is the physician role to make these recommendations.
Additional efforts should be made to discover drugs that can abolish or slow down the apoptosis. Antibodies against PD-L1, FasL, growth factors, or their receptors may be helpful. Forty chemical compounds have inhibitory effects on different steps of apoptosis but may be toxic to normal cells. Phenoxodiol, an isoflavone that targets a regulator of sphingosine kinase depriving the cell of XIAP and FLIP was evaluated for ovarian cancer but was disappointing. Thus, it is essential to discover biologic agents such as antibodies against one or more of the extracellular mediators with better effects and with few or no side effects that will be approved for clinical use to arrest axonal apoptosis at the optic nerve. So far, none has been discovered, and research efforts are mandatory because such molecules may be used in glaucoma as well as other fields to prevent cellular few or no by apoptosis.
Water which is the key element responsible for life in the world is becoming more valuable due to the increased consumption and demand. In order to provide a locally controlled water supply, wastewater recycling offers great environmental advantages. Recycling of water can corporate in decreasing the consumption of water from sensitive ecosystem, reducing the environmental pollution, and even preventing accumulation of pollutants in our ecosystem. The US Environmental Protection Agency (USEPA) has suggested three stages of water recycling; in the primary stage that can be achieved by a sedimentation process, normally the produced water is not suitable for any use. The biological oxidation and disinfection process are used to reach the secondary stage. The produced water from that stage can be used mainly for irrigation of nonfood crop and industrial cooling system. The tertiary stage in wastewater treatment is reached using chemical, coagulation, filtration, and disinfection processes. Produced water in the tertiary stage can be employed mostly for irrigation of food crops and landscape, washing of vehicles, and flushing toilet [1]. Good quality water (i.e., water free of contaminants) is essential to human health and a critical feedstock in a variety of key industries including oil and gas, petrochemicals, pharmaceuticals, and food. The available supplies of water are decreasing due to (1) low precipitation, (2) increased population growth, (3) more strict health-based regulations, and (4) competing demands from a variety of users, e.g., industrial, agricultural, and urban development. In addition, our water today became such type of cocktail of chemicals that has more than 100 of toxic compounds, viruses, bacteria, and metals. Consequently, water scientists and engineers are seeking alternative sources of water and new technologies for wastewater treatment and recycling. These wastewaters include but not limited to sewage effluent, contaminated surface or groundwater, and industrial wastewater. Water recovery-recycle-reuse has proven to be effective and successful in creating a new and reliable water supply while not compromising public health [2].
Water pollution with contaminants became a global issue. Among of these contaminants, heavy metals have a greater concern mainly due to their bioaccumulation, toxicity, and non-biodegradability. Their non-biodegradability nature makes their existence in water to cause great risk to living organisms. Accordingly, many government environmental agencies such the US Environmental Protection Agency (USEPA) and World Health Organization (WHO) have set the maximum acceptable concentration level for heavy metals in recycled water. Therefore, different methodologies, with varying level of success, have been employed to remove these contaminations from water and wastewater. Biological treatment (aerobic and anaerobic), coagulation, precipitation, oxidation, membrane, and filtration are common methods of removing microorganisms and ionic and cationic compounds from wastewater streams. The performance of these methods is generally acceptable at low concentration of heavy metals below few hundred ppm, which is the main drawback of them. Even though most of the wastewater treatment technologies available today are effective, they are often costly and time-consuming methods. Bioadsorption is considered as among the most promising low-cost process for wastewater treatment. Numerous materials were used as adsorbents to remove heavy metal ions from water, such as metal oxides, activated carbon, zeolite, chitin, metal sulfide, resin, etc. The search for new and more effective materials to be used as bioadsorbent materials has a continuous effort and been considered by many researchers. Since 1990 till now, there are more than 5000 publications in the field of bioadsorption of heavy metals, and approximately 6% of these publications have been concerned on using marine algae [3]. Figure 1(a and b) shows the dramatic increase in both the number of publications and their citations versus time.
Histograms for (a) number of publications in the field of biosorption of heavy metals and (b) the number of citations each year on these publication [3].
Marine algae are one of the most highly available natural resources in tropical ecosystem where around 2 million tons of them are collected from seas and oceans and cultured in artificial system [4]. They are useful in different applications such as pharmaceutical, food, and cosmetic industries. Algae have rich biochemical composition; therefore, its biomass is a promising material to be used as bioadsorbent to decontaminate water and wastewater by removing pollutants such as heavy metals [5, 6]. Marine algae are commonly known as seaweeds, and they had a great potential to be used in pollutant removal process as a promising bioadsorbents material. This is due to their renewable availability, distinct properties, and high biosorption capacity. Seaweeds are divided into three main broad groups, namely, (i) green (Chlorophyta), (ii) red (Rhodophyta), and (iii) brown (Phaeophyta) algae. Marine algae have many advantages for bioadsorption. Among them brown algae provided the best adsorption capacities due to their cell wall structure and components. The cell wall of brown algae has a lot of active chemical functional groups such hydroxyl, carboxylic acid, amine, imidazole, phosphate, phenolic, thioether, and sulfhydryl which offer a selective binding and interaction with metals and pollutants in the bioadsorption process. It contains mainly cellulose, a group of salts of sodium, potassium magnesium, and calcium, and alginate, which is a type of polysaccharide (anionic copolymer) [7].
Figure 2 illustrates the main four mechanisms of heavy metal uptake by bioadsorbents. The first one is ion-exchange process including ionic or cationic exchange. The surface of the cell wall contains mainly organic nitrogen group in the case of ionic exchange or hydroxyl and organic sulfate or phosphate in the case of cationic exchange. The uptake mechanism can be a complexation through a covalent or electrostatic interaction where the metal ions form a complex compound with organic molecules. The third mechanism is chelation which involves an interaction between the metal and an organic compound that has more than one electron donor functional group. The last one is through precipitation that occurs when the pH of the solution varies due to cellular metabolism or when the concentration of metals increases [8].
Classification of metal uptake mechanism by bioadsorbents.
Table 1 summarizes some of the marine algae (red, green, and brown), those used for removal of transition, actinide, or lanthanide metals. Many researchers found that the Sargassum brown algae has a high adsorption capacity to remove heavy metals such as Cu, Ni, Cd, Pd, Cr, Sm, and Pr from their solution efficiently due to its cell wall structure that is rich in active bioadsorption sites [9, 10, 15, 17, 18, 19]. Mostly, bioadsorption offers many advantages over the bioaccumulation process since bioadsorbents are available commonly as by-product or waste, as well as they do not need growth media and growth conditions. As a result, they are considered low-cost materials with high possibility to be reused for many cycles. The literatures show that marine algae can be used for the removal of heavy metals in dead or live forms. However, in industrial applications, the nonliving marine algae provide more practical bioadsorbent materials for the removal of pollutants. This is because toxicity of heavy metals and other pollutants do not affect dead biomass. In addition, the performance of those bioadsorbents can be improved by physical treatments such as heating or chemical processing such as acid or base treatments. This enhancement in their biosorption capacity is attributed to activation of the adsorption sites as well as rearrangement of the cell wall structure to be more accessible and compatible for pollutants capturing and removal [35].
Number | Name of algae | Removed metals | Ref. |
---|---|---|---|
1 | Sargassum sp. | Cu | [9] |
2 | Sargassum sp. | Sm and Pr | [10] |
3 | Spirogyra spp. | Cr | [11] |
4 | Sargassum vulgaris | Cd and Ni | [12] |
5 | Sargassum hystrix | Pb | [13] |
6 | Sargassum natans | Pb | [13] |
7 | Sargassum hemiphyllum | Ni and Cu | [14] |
8 | Sargassum wightii | Ni | [15] |
9 | Sargassum sp. | Cr | [15] |
10 | Sargassum honeri and S. hemiphyllum | Ho, Dy, Lu, and Yb | [16] |
11 | Sargassum ilicifolium | Ni and Co | [17] |
12 | Sargassum sp. | La, Nb, Eu, and Gd | [18] |
13 | Sargassum muticum and Fucus spiralis (brown algae) | Pd, Zn, and Cd | [19] |
14 | Fucus vesiculosus (brown algae) | Cu | [20] |
15 | Palmaria palmata (red algae) | Cu | [20] |
16 | Fucus spiralis (brown algae) | Cu | [20] |
17 | Ulva sp. (green algae) | Cu | [20] |
18 | Fucus ceranoides and Fucus serratus (brown algae) | Cd | [21] |
19 | Laminaria japonica | Cd, Pb, and Fe | [22] |
20 | Laminaria japonica (washed or oxidized by potassium permanganate) | Pb | [23] |
21 | Gracilaria fischeri | Cu and Cd | [24] |
22 | Gracilaria sp. | Cd, Cu, Zn, Pb, and Ni | [25] |
Padina sp. | Cd, Cu, Zn, Pb, and Ni | [25] | |
23 | Pilayella littoralis | Cr, Fe, Al, Cd, Cu, Zn, Co, and Ni | [26] |
24 | Cladophora crispata | Pb, Cu, Cd, and Ag | [27] |
25 | Cladophora fascicularis | Cu and Pb | [28] |
26 | Ecklonia sp. | Cr | [29] |
27 | Colpomenia sinuosa | Ni and Cu | [14] |
28 | Petalonia fascia | Ni and Cu | [14] |
29 | Ulva fascia | Ni and Cu | [14] |
30 | Padina pavonica | Ni and Cd | [12] |
31 | Sargassum cymosum | Cr | [30] |
32 | Turbinaria conoides | Pb | [31] |
33 | Laurencia obtusa | Cd, Co, Cr, Cu, and Ni | [32] |
34 | Ulva reticulata | Zn | [33] |
35 | Ascophyllum nodosum Fucus spiralis Laminaria hyperborean Pelvetia canaliculata | Cu, Ni, Zn, and Ca | [34] |
Marine algae used in bioadsorption removal of heavy and lanthanide metals.
An idea about the adsorption process is predicted using the correlation between the pressure or the concentration of adsorbate and the adsorption capacity (X/m) at constant temperature as shown in Figure 3.
Adsorption isotherm.
The amount of adsorbate (X) adsorbed should be normalized by the mass of adsorbent (m) to allow comparison of different materials. From Figure 1, it can be predicted that after the saturation point, the number of adsorption sites on the adsorbent is occupied, and the vacancies became limited so that the adsorption does not occur anymore. There are five general types of adsorption isotherms. They are as follows:
Type I adsorption isotherm (shown in Figure 2)
The main characteristics of this type are (i) there is a monolayer adsorption and (ii) it might be explained using the Langmuir adsorption isotherm.
Type II adsorption isotherm
Figure 4 shows a typical adsorption isotherm curve of type II. This type of adsorption shows a large deviation from the Langmuir isotherm model and a flat region, which is corresponding to a monolayer formation.
Type III adsorption isotherm
Type II adsorption isotherm.
This type of isotherm indicates that there is no flat region as shown in Figure 5, and also there are formations of multilayer adsorption.
Type IV adsorption isotherm
Type III adsorption isotherm.
It can be depicted from Figure 6 that there is a monolayer formation (intermediate region), which is followed by a multilayer formation at certain adsorbate concentration. At low concentration of adsorbate, the adsorption is mostly similar to type II adsorption isotherm.
Type V adsorption isotherm
Type IV adsorption isotherm.
It is similar to type IV with a difference in the range of adsorbate’s concentration where the monolayer and multilayer start the formation as shown in Figure 7.
Type V adsorption isotherm.
The adsorption isotherms usually are being studied to understand the adsorption behavior modulation and to calculate the adsorption capacity for the adsorbents, so the data analysis is done using a linear/nonlinear least squares methods of adsorption isotherms, where they describe the relationship between the adsorbed amount of adsorbate and its equilibrium concentration in the solution.
The Freundlich, Langmuir, Temkin, Sips, and Redlich-Peterson models are the most common types of the adsorption isotherms to describe the metal ion bioadsorption from their single component solution.
The Freundlich isotherm (Eq. 1) is an empirical model where the adsorption occurs on heterogeneous adsorption sites on adsorbent surface, which is the general case in macroalgae bioadsorbents:
where
qe: The adsorption density at equilibrium (mg adsorbate/g of adsorbent).
Ce: The residual adsorbate concentration in the solution (mg/L) at equilibrium.
Kf: The relative adsorption capacity (mg1−1/n11/n/g).
n: The unit less constants reflect the adsorption intensity.
A plot of lnCe against lnqe will give a straight line with a slope 1/n and intercept LnKf. Smaller 1/n greater expected heterogeneity [35]. It is worthy here to note that usually the adsorption data have a good fit with the Freundlich isotherm model due to the well-known insensitivity of its linear form (ln-ln plot).
The Langmuir adsorption isotherms model is considered as the best known for describing a monolayer chemical adsorption process on homogenous adsorption sites on adsorbent surfaces. It partially considers the thermodynamic in the adsorption process. It is expressed in Eq. (2):
where
qe: The adsorption capacity at equilibrium (mg of adsorbate/g of adsorbent).
Ce: The residual adsorbate concentration at equilibrium in solution (mg/L).
qmax: The maximum adsorption capacity corresponding to monolayer coverage (mg of analyte adsorbed/g of adsorbent).
b: The Langmuir constant correlated to the adsorption energy (1/mg adsorbate).
The essential features of the Langmuir isotherm may be expressed in terms of equilibrium parameter RL (Eq. 3), which is a dimensionless constant referred to as separation factor or equilibrium parameter [36]:
The most used linear form of the Langmuir model is the following form (Eq. 4), which is also called reciprocal Langmuir plot:
Plotting Ce/qe versus Ce from the experimental data gives a linear regression where the slope for that plot gives the experimental maximum adsorption capacity qmax, and the intercept gives the Langmuir constant b.
There are another three linear transformation forms of the Langmuir isotherm models: (1) the distribution coefficient or Scatchard plot, (2) Eadie-Hofstee plot, and (3) double reciprocal Lineweaver-Burk plot. Every one of these four linear transformation forms gives a greater weighing to low adsorption values than to high adsorption values, which leads to changing in the error distribution [37].
The energy of adsorption can be described using the Temkin isotherm (Eq. 5). However, this isotherm is valid only for an intermediate range of adsorbate concentrations [38]:
Rearranging Eq. (4) results in Eq. (6):
Plotting qe versus ln(Ce) gives a linear regression where the slope for that plot gives the Temkin isotherm constant (b) and the intercept gives the Temkin isotherm equilibrium binding constant (AT) (L/g), where R is the universal gas constant (8.314 J/mol K), T is the temperature in Kelvin (K), and B in Eq. (7) is a constant related to heat of adsorption (J/mol):
The Sips isotherm model for mono-component system is a combination between the Freundlich and Langmuir isotherm models. Eq. (8) expresses the Sips model:
where
qe: The adsorption capacity at equilibrium (mg of adsorbate/g of adsorbent).
Ce: The residual adsorbate concentration at equilibrium in solution (mg/L).
qmax: The maximum adsorption capacity corresponding to monolayer coverage (mg of analyte adsorbed/g of adsorbent).
b: The Langmuir constant correlated to the adsorption energy (1/mg adsorbate).
ns: The Sips constant for the heterogeneity of binding surface.
As an extension for the Langmuir isotherm, a model with three parameters was established expressed in Eq. (9). That is Redlich-Peterson isotherm:
where Ce (mg/L) is the residual adsorbate concentration at equilibrium in the solution and qe (mg/g) is the adsorption capacity at equilibrium. However, aRP (1/g) and bRP (1/mg)nRP do not have physical or chemical meaning. The third parameter nRP is dimensionless that gives an idea about the heterogeneity of adsorption sites on the surface of adsorbents [39].
Studying the uptake rate of heavy metals is achieved by the adsorption kinetics where the metal ion uptake rate clearly controls residence time of these compounds at the solid-liquid interface, so and in sequence the mechanism of heavy metal adsorption on the biomass materials will be evaluated using the most common kinetic models.
The simplest one which expresses on the proportionality between the metal adsorption and the number of vacant adsorption sites on the surface of adsorbents is Lagergren model (pseudo-first-order). The nonlinear and linear forms of the model are represented in Eqs. (10) and (11), respectively [40]:
where qt and qe (mg/g), respectively, are the adsorption capacity at any time (t) and at equilibrium. k1 (1/min) is the pseudo-first-order rate constant.
The kinetic model that has the correlation between the adsorption of metal ions and the square of active vacant adsorption sites on the surface of adsorbents is called pseudo-second-order rate model (Eq. 12) [38]:
Eq. (8) can be rearranged to be in the following linear form (Eq. 13):
where qt and qe (mg/g), respectively, are the adsorption capacity at any time (t) and at equilibrium. k2 (g/mg min) is the pseudo-second-order rate constant.
By plotting ln(qe−qt) versus t and t/qt versus t in the previous equations (Eqs. (11) and (13)), all the adsorption kinetic parameters can be determined from the slope and the intercept.
The influence of mass transfer resistance on binding metal ions on adsorbents was tested using the intra-particle diffusion model (Weber and Morris model) represented in Eq. (14) [41]:
where qt (mg/g) is the adsorption capacity at any time (t), kid (mg/g min0.5) is the intra-particle diffusion rate constant, and C (mg/g) is a constant related to the thickness of the boundary layer. From plotting of qt versus the square root of t, the diffusion constant kid can be calculated. If this plot passes through the origin, then intra-particle diffusion is the only rate-controlling step.
Removal of heavy metals from wastewater would provide an exceptional alternative water resource. Algae biomass adsorbents, which utilized for adsorptive removal of heavy metal pollutants from wastewater, show a promising alternative. Different empirical isotherm models for single analyte have been discussed (i.e., Freundlich, Langmuir, Temkin, Sips, and Redlich-Peterson). In a large number of studies, the Freundlich and Langmuir models are the most commonly and widely used isotherm models. The two kinetic models, which are still in a wide use for studying the rate uptake of heavy metals and their bioadsorption from aqueous solutions, are pseudo-first- and pseudo-second-order kinetic models. In chemisorption process, the pseudo-second-order kinetic model is superior to pseudo-first-order model as it takes into account the interaction of adsorbent-adsorbate through their valency forces.
The support of the Center for Environment and Water in the research institute of King Fahd University of Petroleum and Minerals King Fahd University of Petroleum and Minerals is highly acknowledged.
The author declares that there are no conflicts of interest.
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