In this work, we prepared an adsorbent composed of the cationic N,N-dimethylamino propylacrylamide methyl chloride quaternary (DMAPAAQ) polymer gel and iron hydroxide for adsorbing arsenic from groundwater. The gel was prepared via a novel method designed to ensure the maximum content of iron particles in its structure.
In this work, we prepared an adsorbent composed of a cationic polymer gel containing iron hydroxide in its structure designed to adsorb arsenic from groundwater. The gel we selected was the N,N-dimethylamino propylacrylamide methyl chloride quaternary (DMAPAAQ) gel. The objective of our preparation method was to ensure the maximum content of iron hydroxide in the structure of the gel. This design approach enabled simultaneous adsorption by both the polymer structure of the gel and the iron hydroxide component, thus, enhancing the adsorption capacity of the material. To examine the performance of the gel, we measured reaction kinetics, carried out pH sensitivity and selectivity analyses, monitored arsenic adsorption performance, and conducted regeneration experiments. We determined that the gel undergoes a chemisorption process and reaches equilibrium at 10 h. Moreover, the gel adsorbed arsenic effectively at neutral pH levels and selectively in complex ion environments, achieving a maximum adsorption volume of 1.63 mM/g. The gel could be regenerated with 87.6% efficiency and NaCl could be used for desorption instead of harmful NaOH. Taken together, the presented gel-based design method is an effective approach for constructing high-performance arsenic adsorbents.
Water pollution is a great environmental concern, motivating researchers to develop methods for removing contaminants such as arsenic from wastewaster1. Among all the reported methods, adsorption processes are a relatively low cost approach for heavy metal removal2,3,4,5,6,7. Iron oxyhydroxide powders are considered to be one of the most efficient adsorbents for extracting arsenic from aqueous solutions8,9. Still, these materials suffer from a number of drawbacks, including early saturation times and toxic synthetic precursors. Additionally, there is a severe adverse effect in the water quality when these adsorbents are used for a long period of time10. An additional separation process, such as sedimentation or filtration, is then needed to purify the contaminated water, which increases the cost of the production further8,11.
Recently, researchers have developed polymer gels such as cationic hydrogels, microgels, and cryogels that have demonstrated efficient adsorption properties. For example, an arsenic removal rate of 96% was achieved by the cationic cryogel, poly(3-acrylamidopropyl) trimethyl ammonium chloride [p(APTMACl)]12. Additionally, at pH 9, approximately 99.7% removal efficiency was achieved by this cationic hydrogel13. At pH 4, 98.72 mg/g of maximum arsenic adsorption capacity was achieved by the microgel, based on tris(2-aminoethyl) amine (TAEA) and glyceroldiglycidyl ether (GDE), p(TAEA-co-GDE)14. Although these gels demonstrated good adsorption performances, they failed to effectively remove arsenic from water at neutral pH levels, and their selectivities in all studied environments were not reported15. A maximum adsorption capacity of 227 μg/g of was measured when Fe(III)-Sn(IV) mixed binary oxide-coated sand was used at a temperature of 313 K and a pH of 716. Alternatively, Fe-Zr binary oxide-coated sand (IZBOCS) has also been used to remove arsenic and achieved a maximum adsorption capacity of 84.75 mg/g at 318 K and a pH of 717. Other reported adsorbents suffer from low adsorption performances, lack of recyclability, low stability, high operational and maintenance costs, and the use of hazardous chemicals in the synthesis process4.
We sought to address the above limitations by developing a material with improved arsenic adsorption performance, high selectivity in complex environments, recycling capability, and efficient activity at neutral pH levels. Therefore, we developed a cationic gel composite of N,N-dimethylamino propylacrylamide methyl chloride quaternary (DMAPAAQ) gel and iron(III) hydroxide (FeOOH) particles as an adsorbent for arsenic removal. We chose to combine FeOOH with our gel because FeOOH increases the adsorption of both forms of arsenic18. In this study, our gel composite was designed to be non-porous and was impregnated with FeOOH during preparation. In the next section, the details of the gel preparation method, including our strategy for maximizing the content of FeOOH is discussed further.
CAUTION: Arsenic is extremely toxic. Please use gloves, long sleeve clothing, and experimental goggles at all times during the experiment to prevent any contact of arsenic solution with the skin and eyes. If arsenic comes into contact with any part of your body, wash it immediately with soap. Additionally, please clean up the experimental surroundings regularly so that you and others do not come into contact with arsenic, even when the experiment is not being performed. The symptoms of arsenic exposure may appear after a long period of time. Prior to cleaning the equipment, first rinse it with clean water and dispose the water separately into an experimental waste container designated for arsenic. Then, clean the equipment well with detergent. To prevent arsenic contamination of the environment, take precautions while disposing of arsenic samples. Dispose of them separately into experimental waste containers designated for arsenic. After the adsorption or desorption experiment is performed, the gels contain a high amount of arsenic. Therefore, dispose of the gels separately to a designated experimental waste bin for only arsenic-containing gels.
1. Synthesis of the DMAPAAQ+FeOOH gel composite
2. pH sensitivity analyses
3. Arsenic adsorption experiment
4. Selectivity analyses of the DMAPAAQ+FeOOH gel
5. Equilibrium rate analyses
6. Regeneration analysis
Figure 1 describes the experimental setup for the preparation of the DMAPAAQ+FeOOH gel. Table 1 illustrates the compositions of the materials involved in the preparation of the gel.
Figure 2 shows the relation of contact time with the adsorption of arsenic by the DMAPAAQ+FeOOH gel. In the figure, the amount of adsorption of arsenic was examined at 0.5, 1, 3, 7, 11, 24, and 48 h. The results show that the adsorption of arsenic reaches its equilibrium after 10 h, and after 24 h of adsorption, minimal increase in the amount of adsorption of arsenic was detected.
Figure 3a,b shows the pseudo first order and pseudo second order reaction kinetics for arsenic adsorption by the DMAPAAQ+FeOOH gel. The results suggest that the correlation coefficients (R2) for pseudo first order and pseudo second order were 0.866 and 0.999, respectively.
Figure 4 shows the pH sensitivity of the DMAPAAQ+FeOOH gel. The same amount of dry DMAPAAQ+FeOOH gel (20 mg) was immersed in arsenic solutions (0.2 mM) at different pH levels for 24 h at 20 °C and 120 rpm. The results suggest that the adsorption of arsenic was high at low and neutral pH levels and low at high pH levels.
Figure 5 shows the adsorption performance of DMAPAAQ+FeOOH. The same amount of dry DMAPAAQ+FeOOH gel (20 mg) was immersed in different arsenic solution concentrations (0.1, 0.2, 0.5. 1, 2 mM) at 20 °C and 120 rpm for 24 h. The results show that the maximum arsenic adsorption capacity of the DMAPAAQ+FeOOH gel was 1.63 mM/g. The data were also consistent with the Langmuir isotherm.
Figure 6 shows the selectivity analysis of the DMAPAAQ+FeOOH gel. The same amount of dry DMAPAAQ+FeOOH gel (20 mg) was immersed in the arsenic solution (0.2 mM) with different SO42− concentrations (1, 2, 5, 10, 20 mM) at 20 °C and 120 rpm for 24 h. The analysis shows that the adsorption amount of arsenic decreased slightly with an increase in SO42− concentration; however, the change was small, and at high concentrations of SO42−, the gel still adsorbed arsenic effectively.
Figure 7 shows the regeneration experiment of the DMAPAAQ+FeOOH gel. The same amount of dry gel (20 mg) was used for eight consecutive days of experimentation. The experiment was conducted using a 0.2 mM arsenic solution at 20 °C and 120 rpm for 24 h. To perform the desorption process, the gel was then washed and immersed into a 0.5 M NaCl solution at 20 °C and 120 rpm for 24 h. The gel was regenerated successfully after eight days of continuous adsorption-desorption cycles. We calculated the regeneration efficiency from the adsorption data on day 1 and day 7; a regeneration efficiency of 87.6% was achieved.
Chemical | Quantity (mol/m3) | |
Monomer | DMAPAAQ | 500 |
Crosslinker | MBAA | 50 |
Accelerator | Sodium Sulfite | 80 |
Sodium Hydroxide (NaOH) | 2100 | |
Initiator | Ammonium peroxodisulfate (APS) | 30 |
Ferric Chloride (FeCl3) | 700 |
Table 1: Composition of the DMAPAAQ+FeOOH gel. This table has been adopted from Chemosphere [217, 808-815, doi: 10.1016/j.chemosphere.2018.11.050 (2019)]15 and details the materials used in preparing the DMAPAAQ+FeOOH gel.
Figure 1: Experimental setup for preparing the DMAPAAQ+FeOOH gel. This figure shows the arrangement of equipment for preparing the DMAPAAQ+FeOOH gel. Since our preparation method is unique, this figure will help researchers replicate our setup. Please click here to view a larger version of this figure.
Figure 2: Relating the contact time with the adsorption amount between the DMAPAAQ+FeOOH gel and arsenic solution. This figure has been modified from Chemosphere [217, 808-815, doi: 10.1016/j.chemosphere.2018.11.050 (2019)]15 and shows the relationship between the adsorption amount of arsenic by the DMAPAAQ+FeOOH gel and the contact time. Additionally, it illustrates the time required for the gel to reach its adsorption equilibrium. Please click here to view a larger version of this figure.
Figure 3: Arsenic adsorption reaction kinetics of the DMAPAAQ+FeOOH gel. (a) Pseudo first order. (b) Pseudo second order. This figure has been modified from Chemosphere [217, 808-815, doi: 10.1016/j.chemosphere.2018.11.050 (2019)]15 and shows the suitability of the kinetic model to the DMAPAAQ+FeOOH gel. Please click here to view a larger version of this figure.
Figure 4: pH sensitivity analysis of the DMAPAAQ+FeOOH gel. This figure has been adopted from Chemosphere [217, 808-815, doi: 10.1016/j.chemosphere.2018.11.050 (2019)]15 and shows the results of the pH sensitivity analysis of the DMAPAAQ+FeOOH gel in arsenic solutions. Please click here to view a larger version of this figure.
Figure 5: Adsorption performance of the DMAPAAQ+FeOOH gel. This figure has been modified from Chemosphere [217, 808-815, doi: 10.1016/j.chemosphere.2018.11.050 (2019)]15 and shows the arsenic adsorption amount by the DMAPAAQ+FeOOH gel at different concentrations of arsenic and the fitting of these data with the Langmuir isotherm model. Please click here to view a larger version of this figure.
Figure 6: Selectivity analysis of the DMAPAAQ+FeOOH gel. This figure has been modified from Chemosphere [217, 808-815, doi: 10.1016/j.chemosphere.2018.11.050 (2019)]15 and shows the arsenic adsorption selectivity of the DMAPAAQ+FeOOH gel in the presence of different concentrations of sulfate ions. Please click here to view a larger version of this figure.
Figure 7: Regeneration analysis of the DMAPAAQ+FeOOH gel. This figure has been adopted from Chemosphere [217, 808-815, doi: 10.1016/j.chemosphere.2018.11.050 (2019)]15. The reusability of the DMAPAAQ+FeOOH gel was examined for eight continuous days using arsenic solutions for adsorption and NaCl for desorption processes. Please click here to view a larger version of this figure.
The main advancement of our developed method is the unique design strategy of the gel composite. The purpose of our gel preparation method was to maximize the amount of iron content in the gel. During the preparation, we added FeCl3 and NaOH to the “initiator solution” and the “monomer solution,” respectively. Once the monomer solution was mixed with the initiator solution, there was a reaction between FeCl3 and NaOH, producing FeOOH inside the gel. This phenomenon ensured maximum iron content in the gel composite. Despite the advantages of this method, the gel does not form under the following conditions: 1) When the solutions are not mixed thoroughly; 2) When the amount of FeCl3 exceeds 700 mol/m3 or the initiator, APS, and the accelerator, sodium sulfite, are lower.
If the gel does not form, add the initiator and accelerator gradually and mix the solution thoroughly. If the amount of initiator and accelerator are too high, the polymer structure of the gel differs, and the desired performance cannot be achieved. When the gel starts forming, stop mixing it to avoid distorting the gel.
Previous studies have reported ineffective adsorption of arsenic at neutral pH levels. Thus, the pH sensitivity experiment in the present work was important for indicating the practical applicability of the developed gel. Our studies demonstrate that the gel adsorbed arsenic effectively and was regenerated by NaCl at neutral pH levels. Although the adsorption amount of arsenic was high at acidic pH values and low at basic pH values, the adsorption was effective at neutral pH levels (Figure 4). To assess the adsorption behavior under real-life conditions, we conducted other experiments at neutral pH levels.
The relationship between the gel/arsenic solution contact times and arsenic adsorption amount was studied. The DMAPAAQ+FeOOH gel achieved adsorption equilibrium at 10 h (Figure 2). Additionally, we examined the rate of adsorption by the DMAPAAQ+FeOOH gel with the two kinetic models, pseudo first order and pseudo second order (Figure 3a,b). The correlation coefficients (R2) denoted the similarity between the experimental values and calculated values. We found that the R2 value was higher for the pseudo second order reaction kinetics. This finding suggests that the adsorption between the arsenic solution and DMAPAAQ+FeOOH gel is a chemisorption process19.
We performed the adsorption performance analyses at neutral pH levels. 20 mg of dry gel was immersed in the arsenic solution for 24 h at different concentrations of As(V). Figure 5 shows the amounts of arsenic adsorbed by the DMAPAAQ+FeOOH gel. These results were consistent with the Langmuir isotherm model of adsorption. The maximum adsorption amount by the gel reached 1.63 mM/g (Figure 5). Notably, the developed gel outperformed previously reported adsorbents studied at neutral pH levels. We rationalize this observation by the unique structure of the gel, which enables simultaneous arsenic adsorption by both the DMAPAAQ and FeOOH units. We found that 35.5% of arsenic was adsorbed by the amino group of the DMAPAAQ+FeOOH composite and 64.4% of arsenic was adsorbed by FeOOH particles15. During the adsorption process, make sure that the gel is immersed into the arsenic solution completely. The high levels of arsenic adsorption by the current gel over conventional and recently studied materials demonstrate its promising utility as a highly efficient adsorbent.
Selectivity is an important property of an adsorbent because there are many competing ions in water, including Cl−, HS−, SO32−, SO42−, H2CO3, HCO3−, and CO32− 20. The Hofmeister series suggests that the sulfate ion (SO42−) can disrupt hydrocarbon packing and penetrate the headgroup region of the monolayer of an adsorbent21. The concentration of sulfate in groundwater has been determined to be as high as 230 mg/L22. Therefore, if the developed gel can selectively adsorb arsenic with sulfate as a competing ion, it may be suitable for treating environmental groundwater. Thus, selectivity analyses with sulfate ions were performed and showed that the DMAPAAQ+FeOOH gel adsorbed arsenic effectively at high concentrations of sulfate (Figure 6). Since the adsorption amount of arsenic was similar in the absence or presence of sulfate ions, the gel may perform as effectively in groundwater as in the laboratory.
Regeneration is an important feature of any practical adsorbent because it ensures cost reductions, eco-friendliness, and usability23. The developed gel was regenerated successfully for eight consecutive days of experimentation (Figure 7). Additionally, 87.6% regeneration efficiency was achieved when the same gel was used for all eight adsorption-desorption cycles. One of the most important findings of our research was the use of NaCl in the desorption process. While NaOH is conventionally used for desorption, it can be harmful to human health. Therefore, we substituted NaOH for NaCl in our studies, which had not been reported previously.
The authors have nothing to disclose.
This research was supported by the JSPS KAKENHI Grant Number (26420764, JP17K06892). The contribution of Ministry of Land, Insfrastructure, Transport and Tourism (MLIT), Government of Japan under ‘Construction Technology Research and Development Subsidy Program’ to this research is also recognized. We also acknowledge the contribution of Mr. Kiyotaka Senmoto to this research. Ms. Adele Pitkeathly, Senior Writing Advisor Fellow from Writing Center of Hiroshima University is also acknowledged for English corrections and suggestions. This research was selected for oral presentation in 7th IWA-Aspire Conference, 2017 and Water and Environment Technology Conference, 2018.
N,N’-dimethylamino propylacrylamide, methyl chloride quaternary (DMAPAAQ) (75% in H2O) | KJ Chemicals Corporation, Japan | 150707 | |
N,N’-Methylene bisacrylamide (MBAA) | Sigma-Aldrich, USA | 1002040622 | |
Sodium sulfite (Na2SO3) | Nacalai Tesque, Inc., Japan | 31922-25 | |
Sodium sulfate (Na2SO4) | Nacalai Tesque, Inc., Japan | 31916-15 | |
Di-sodium hydrogenarsenate heptahydrate(Na2HAsO4.7H20) | Nacalai Tesque, Inc., Japan | 10048-95-0 | |
Ferric chloride(FeCl3) | Nacalai Tesque, Inc., Japan | 19432-25 | |
Sodium hydroxide(NaOH) | Kishida Chemicals Corporation, Japan | 000-75165 | |
Ammonium peroxodisulfate (APS) | Kanto Chemical Co. Inc., Japan | 907W2052 | |
Hydrochloric acid (HCl) | Kanto Chemical Co. Inc., Japan | 18078-01 | |
Sodium Chloride (NaCl) | Nacalai Tesque, Inc., Japan | 31320-05 |