Natural product based composite for extraction of arsenic (III) from waste water
© The Author(s) 2017
Received: 24 October 2016
Accepted: 28 March 2017
Published: 12 April 2017
In recent years, there has been an increasing concern of environmental pollution and public health issues associated with heavy metals. Sources of heavy metals has risen dramatically to include mining, industrial, medical, agricultural, household chemicals, and others . Among the metal that raise serious concerns are Hg, Cr, Ni, Zn, Cu, AS, and Cd .
The main source of the heavy metals in wastewaters are industrial discharges and household chemical.
Heavy metals in the ground and waste water are usually present in the form of inorganic complexes. The complexes ligands are unlikely to be organic, as they are non-biodegradable.
Several processes for removing heavy metals from waste water have been developed. Among these are chemical electrode solvent extraction, ion-exchange, activated carbon adsorption, precipitation and adsorption [3, 4]. The adsorption received the highest attention since it is simple, inexpensive, and effective especially in wastewater [5, 6].
Nanotechnology is one of the most promising techniques for metal removal from waste water. Nanoparticles have high surface area to volume ratio which provides optimum kinetics for metal binding [7, 8].
Among the above mentioned toxic heavy metals, arsenic has received the most attention and concern, because it is highly toxic and cause chronic effects on human health [9–11]. Arsenic presents in four oxidation states −3, 0, +3 and +5. The most abundant forms of arsenic in soil and waste water are with +3 and +5 oxidation states. An example of As(V) is H3AsO4 and of AS(III) is H3AsO3 . Inorganic arsenic compounds are more toxic than organic arsenic ones, and As(III) is more toxic than As(V) . Environment contamination of arsenic mainly comes from production and use of pesticides and other materials such as glass, paper and semiconductors. Pesticides are considered the major source of arsenic compounds in wastewater and ground. Examples on these pesticides are disodium methane arsenate (DSMA), lead arsenate, Ca3AsO4, monosodium methane arsenate (MSMA), copper acetoarsenite, cacodylic acid (used in process of cotton production) and arsenic acid (H3AsO4) [14, 15].
The major concern aroused when high concentrations of arsenic was detected in the ground and surface water at several regions of the world, including India, Bangladesh, Taiwan, Chile, Western United States, and Vietnam . Several methods are known to be effective in removing arsenic such as: coagulation, precipitation, chromatography, adsorption, and co-precipitation. The adsorption is process involves the adsorption of arsenic on alumina and active carbon . Adsorption process is the most effective and most widely used. Since, low cost materials such as hydroxyapatite, clay, agricultural residues and activated charcoal are used in this process .
Recently, several publications showed the possibility of using calcium phosphates hydroxyapatite (HAp) biomaterials composites as an adsorbent for heavy metals [18–21] and residual pesticides  from water and land. It was chosen because of is has highly porous structure. Unfortunately, it was found that, HAp has low adsorption capacity for metal, this was attributed to the limited number of coordination sites on HAp. So the use of HAp as a metal adsorbent was very limited. Its highly porous structure makes it unique and attractive for. One approach taking advantage of its highly porous structure and enhancing its adsorbent efficiency for metals is by blending it with a material that has good chemical affinity for hydroxyapatite and metals. Gum Arabic was chosen for this purpose.
Gum Arabic (GA) is a mixture of polysaccharides and inorganic salts. The inorganic salts composed of calcium, magnesium and potassium. The polysaccharide part composed of a skeleton and side chains. The skeleton consist of the repeat unit β-d-galactopyranosyl 1.3 and the side chains are composed of two five units of β-d-galactopyranosyl 1.3, that are attached to the main chain by 1.6 links. Gum Arabic (GA) is a well-known natural material with large number of applications. It is widely used in the pharmaceutical, cosmetic and food industries. It was also used as an emulsifier and stabilizer. In some developing countries GA is used to treat chronic kidney disease .
Recently, the use of GA has been extended to the nanotechnology and nanomedicine fields. Since it is biocompatible for in vivo applications and can stabilize the nanostructures. The branching and its high contents of galactose makes it interacts well with the asialoglyco protein receptors of hepatocytes. GA has been probed for coating and increasing the biocompatibility (in vitro and in vivo studies) of iron oxide magnetic nanoparticles , gold nanoparticles , carbon nanotubes  and quantum dot nanocolloids .
In this work various composites of hydroxyapatite (HAp) and Gum arabic were prepared and evaluated by various spectroscopic and analytical techniques. Hydroxyapatite and GA composite is bio-based and have unique properties such as biocompatibility, bioactivity and osteo-conductivity. These properties make it attractive various applications such as metals extractions. The composite was prepared by the solution method. The possibility of using the prepared composite as a based stationary phase for removal of arsenic (III) from waste water was evaluated. The composite offered in this work could be a very promising adsorbent for arsenic (III).
Gum Arabic (GA) was obtained from the southern area of Morocco: Laayoune-Smara. The Ca(NO3)2*4H2O (99%), (NH4)2HPO4 (99%) were purchased from Aldrich in high purity forms and used as re. Muller-Hinton as received. (Biokar); Muller-Hinton broth (Biokar); potato dextrose agar (PDA), sterile distilled water, and sterile paper discs were used in this work. All synthesis and testing procedure were carried out in triplicates.
Synthesis of HAp/GA composite
Quantities of reagents used in the preparation of the composite
Characterization of the composite
The produced composite was analyzed by infrared spectroscopy (ATR FT-IR), using a Schimadzu FT-IR 300 series instrument (Shimadzu Scientific Instruments). FTIR spectra were acquired over the region 400–4000 cm−1. 1.0 mg of powder samples were mixed with 200.0 mg of KBr (spectroscopic grade) using a mortar, then pressed to form a pellet. The composite structure was also evaluated by X-ray diffraction (XRD) using a Rich Siefert 3000 diffractometer (Seifert, Germany) with Cu–K [(Seifert, Germany) wi8A]. Emission scanning electron microscopy (SEM) was used to investigate the morphology of the prepared composites and the filler/matrix interface by using an SU 8020, 3.0 kV SE(U).
Swelling and biodegradability of the composites
Adsorption of arsenic
The experiment was carried out in a polyethylene beaker that was rinsed with ultrapure water. To the beaker was added an aqueous solution of arsenic with various concentrations (2, 5 and 10 mg/L). To the solution in the beaker was added a sample of the composite (200.0 mg). The produced mixture was stirred for various time periods (15, 30, 45, 60, 120, 180 and 240 min). The mixture was the filtered through a glass funnel fitted with a filter paper and rinsed with ultrapure water. The filtrate from the rinse (50 mL) was collected in a separate test tube and acidified with 500 μL of pure nitric acid. The produced acidic solution was subjected to analysis by Atomic Emission Spectrometry (ICP, AES Ultima 2-JobinYvon). The beak area represents the arsenic was used to determine the concentration of arsenic from a pre-prepared calibration curve.
Adsorption experiments and kinetic parameter
Process of adsorption
Kinetic models of arsenic (III) adsorption
The pseudo first-order model:
The pseudo second-order model:
Intra-particle diffusion model:
Antibacterial and antifungal tests
This study was carried out using the disc diffusion method using three bacterial strains Micrococcus luteus, E. coli and Bacillus subtilis.
The Disc diffusion method for antimicrobial susceptibility testing was carried out according to a standard method by Bauer et al.  to assess the presence of antibacterial activities of the Hap/GA composite. A bacteria culture (which has been adjusted to 0.5 McFarland standard), was used to lawn Muller Hinton agar plates evenly using a sterile swab. The plates were dried for 15 min and then used for the sensitivity test. To the discs were added known weight of HAp/GA composite powder and placed on the Mueller–Hinton agar surface. Each test plate comprises of six discs: A positive control (Tetracycline 1 mg/mL), a negative control (DMSO), and four treated discs. All plate discs were placed in a plate about equidistant to each other. The plate was then incubated for a period of time depends on bacteria cell type M. luteus and E. coli were incubated at 37 °C and at B. subtilis at 33 °C for 18 to 24 h. On the other side, the plate of the fungi Candida albicans contained PDA (potato dextrose agar) was incubated at 37 °C for 48 h, cycloheximide was utilized as an antifungal control. After incubation, the inhibition zone was measured using a caliper. The test was repeated three times to ensure reliability.
Results and discussion
The IR spectrum of HAp is shown in Fig. 2a. The spectrum shows the presence of a band at 3400 cm−1 which corresponds to the OH bond vibration. The bands shows between 1100–900 cm−1 (especially the bands located at 1090, 1050 and 962 cm−1) and 600–500 cm−1 (particularly the bands located at 603 and 571 cm−1) could be attributed to PO4 3− apatitic .
The FT-IR of the HAp/GA composite (Fig. 2b) shows a band near 1683 cm−1 which could be related to the CO stretching vibration. The peaks at 1420 cm−1 could be assigned to the asymmetric and symmetric stretching vibrations of the carboxylate group. The interaction between the COOH of GA and OH of HAp is probably responsible for the appearance of this new very low bandwidth. In addition, the composite IR spectrum shows an absorption band at 3550 cm−1 corresponding to the hydroxyl group.
Microscopic observation SEM
Swelling and biodegradability of HAp/GA composite
The results show that, the loss in the weight of the composite increased by increasing the amount of HAp in the composite. The surface became coarser, more porous and absorbed more water. Figure 6a clearly shows that, the water absorption and the rate of degradation of the composite materials increased by increasing HAp content. The weight loss of the composite HAp/GA immersed in PBS were as follows: after 1 h of immersion the weight loss of the composite HAp/GA with 70/30 was about 12.61%. Composite with a 50/50 composition showed a weight loss of 11.81% after 24 h of immersion. The 70/30 composites showed a loss of 41.56%, and the 60/40 composite showed a loss of 31.92%. Composites with 70% HAp and 30% GA lost about 41.56% of their weights after 24 h, then a slight increasing in mass was noticed (Fig. 6b).
Total organic carbon production
After 24 h of contact time between arsenic (III) solution and the composite HAp/GA, it was found that, the coefficient of the equation of the isotherm Dubinin–Radushkevich is greater than the coefficient values (R2) obtained from Freundlich equation ETDE Langmuir. The values of K and QDR were obtained from Dubinin–Radushkevich isotherm and were equal respectively to −0.0079 kJ2/mole and 3.5243 mg/g, with R2 equal to 0.8831. Therefore, the Dubinin–Radushkevich model is reversible, which implies that the saturation composite sites of HAp/GA by the As(III) ions is complete. These results indicate as shown above that, the interactions between the composite HAp/GA and the adsorbate is a physical–chemical.
Kinetic models of arsenic (III)
The characteristics of adsorption surface
Antibacterial and antifungal test
Diameter of inhibition (mm) of the prepared composites tested on three bacteria and one fungus
The composite (HAp/GA 60/40) showed also antifungal activity with a diameter of inhibition on Candida albicans of about 6.0 mm. The composites showed a lower diameter of inhibition when compared to the positive control, which showed 25.0 mm for M. luteus, 25.0 mm for B. subtilis, 26.0 mm for E. coli, and 25.0 mm for Candida.
All other composites (50/50, 60/40, 70/30 and HAp) didn’t show any activity against the tested bacterial strains and fungi.
Several HAp/GA composites with various weight ratios were prepared by the solution method. The prepared composites were evaluated by various spectroscopic and analytical methods such as Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM). The analysis results showed that, the interaction between the components of the composite was facilitated by H-bonding. The prepared composites were designed to extract the toxic metal arsenic (III) from an aqueous solution. The effects of arsenic concentration, contact time (t) and the complexing nature of HAp/GA composite on the adsorption rate arsenic (III) were evaluated. The three adsorption isotherms: Langmuir, Freundlich and Dubinin Radushkevich were applied to study the mechanism involved in the adsorption of arsenic (III) by the composite. The adsorption kinetic showed that, the adsorption of arsenic (III) on the HAp/GA composite was controlled by two main factors the initial concentration of arsenic (III) and the contact time. The kinetic studies showed that, the rate of adsorption of arsenic (III) by the composites is a second order. Results further showed that some of the HAp/GA composites have activities against antimicrobial and antifungal. The composites offered in this study could be a valuable approach for removing toxic metals for contaminated water.
NA, BR and KA did most of the expérimental work. OH and AL did the spectroscopic analysis including SEM and FT-IR. MR, EM and BH did the isotherm analysis. SJ and WJ wrote the manuscript and put every thing together. MB and LL did Antibacterial and antifungal test. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
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