Abstract

In the present study, continuous-flow column experiments (using glass column, Tygon tubing, and peristaltic pump Manostat Carter) were conducted to investigate the performance of permeable sorption barriers for the removal of cadmium and zinc from synthetic groundwater. Zeolite, ion-exchange resin and granular activated carbon as reactive materials were used. The effectiveness and stability of reactive materials were studied by monitoring of changes of metal ions concentration and selected background anions and cations concentration in groundwater during its flow through columns. Results showed that ion exchange resin was the most effective material of permeable reactive barrier (PRB). Performance of resin barrier remained effective (>99.5% metal ions removal) for the time corresponding to on average of about 10,000 min. The high efficiency of ion-exchange resin in PRB for removal of heavy metals from groundwater was coupled with its reactivity and long barrier lifetime. The breakthroughs in the column tests on activated carbon and zeolite using synthetic groundwater occurred much earlier as compared to resin. Therefore, the system using resin requires smaller amount to treat a given volume of groundwater as compared to other materials. Moreover, the presence of other ions did not impact on activity and permeability of barrier filled with resin.

INTRODUCTION

Many toxic heavy metals have been discharged into the environment as industrial wastes, causing serious soil and water pollution (Inglezakis et al. 2003). They are also common groundwater contaminants at industrial and military installations (Erdem et al. 2004). More strict environmental regulations on the discharge of heavy metals require developing various technologies for their removal (Kocaoba 2007). Groundwater contaminated with heavy metals can typically be treated by ‘pump and treat’, but this remediation approach is neither cost effective nor sustainable. Permeable reactive barriers (PRBs) have recently become established as a promising alternative for the in situ sustainable treatment of groundwater contaminated with heavy metals. A permeable reactive barrier (PRB) is installed in an aquifer perpendicular to the groundwater flow direction (Figure 1). Heavy metals can be immobilized onto the reactive material contained in the treatment wall (barrier) by, for example, sorption including adsorption, ion exchange and/or complexation processes (Hashim et al. 2011; Obiri-Nyarko et al. 2014).

Figure 1

The concept of a permeable reactive barrier (PRB).

Figure 1

The concept of a permeable reactive barrier (PRB).

The choice of PRBs sorption material depends on the type and concentration of heavy metals and their forms present in groundwater. The most commonly used are: granular activated carbon (GAC), zeolites, and ion exchange resins (Barton et al. 2004; Thiruvenkatachari et al. 2008; Hashim et al. 2011; Pawluk & Fronczyk 2015).

GAC was reported to be effective material for removal of heavy metals in PRBs due to its large surface area (about 1,000 m2/g), presence of different types of surface functional groups (e.g. hydroxyl, carbonyl, lactone, carboxylic acid), good mechanical and chemical stability, as well as ability to regeneration and reuse (Thiruvenkatachari et al. 2008; Hashim et al. 2011; Pawluk & Fronczyk 2015). Van Roy et al. (2006) found high efficiency (>99%) of Cd ions removal from contaminated groundwater using GAC. Also, Jusoh et al. (2007) noted a high reduction of Cd and Pb ions concentration resulted from the 2-h water flow through the GAC packed column; the concentration of Cd and Pb ions in water decreased from 20 to 0.0047 and 0.0987 mg/dm3, respectively. The removal of heavy metals using GAC is mainly due to adsorption by porous and/or high surface area of this material (Obiri-Nyarko et al. 2014).

In turn, zeolites are tectosilicate minerals with 3D aluminosilicate structure containing water molecules, alkali and alkaline earth metals in their structural framework (Hashim et al. 2011; Zawierucha & Malina 2014). They have potentials to be used for removal of heavy metals in the PRBs due to high ion exchange, adsorbing, catalytic and molecular sieving capacities (Lee et al. 2010; Misaelides 2011; Zawierucha & Malina 2014). Sorption capacity of zeolites for metal ions decreases with increasing metal concentration in aqueous solutions (Erdem et al. 2004). In turn selectivity of zeolites is affected by the acidity of water (Inglezakis et al. 2003). Moreover, the efficiency of metal ions removal by zeolite increases with the degree of water mineralization (Jarvis et al. 2006), and reduction of particle size results in better process efficiency (Jun et al. 2009). In literature there are many examples of application of natural zeolites for remediation of groundwater or acid mine drainage contaminated with metal ions (Ruggieri et al. 2008; Baker et al. 2009; Lee et al. 2010; Wang & Peng 2010; Zawierucha & Malina 2014).

Ion exchange resins can exchange their mobile ions for ions of similar charge from the surrounding medium (Xiong & Yao 2009). These adsorbents are formed of matrix from polymeric material, to which functional ion groups of an acid, basic or chelate-forming nature are added. Resins are distinguished on the basis of this functionality: cation exchange resins, anion exchange resins or chelating resins. Certain general rules for cation exchange are: (i) the exchanger prefers ions of high charge, (ii) ions of small hydrated volume are preferred and (iii) ions, which interacts strongly with the functional groups of the exchangers are preferred (Fernandez et al. 2005; Gode & Pehlivan 2006). A number of investigators have studied the effectivity of removing metal ions from aqueous solution using different ion exchange resins (Gode & Pehlivan 2006; Pehlivan & Altun 2006, 2007; Cavaco et al. 2007; Xiong & Yao 2009). Nevertheless ion exchange resins have not been a popular choice for use as the PRB material because they are expensive compared with other materials (e.g. zero-valent iron and zeolites). However, they have high capacities, fast reaction rates and high selectivity. In addition, a system using resins can be significantly smaller compared to other materials (Barton et al. 2004; Phillips et al. 2008). Moreover, some resins (e.g. Diphonix and Chelex-100) are less prone to interference from background anions and cations in contaminated groundwater (Phillips et al. 2008), thus can favorably impact on activity and permeability of PRBs due to reduction of potential precipitation of groundwater constituents into a reactive barrier.

The objectives of this study were to evaluate efficiency of PRBs filled with sorption materials (GAC, zeolite, ion-exchange resin) for the removal of Cd and Zn ions from groundwater, comparative analysis of used materials, and to assess the long-term performance of such treatment systems. The impact of selected groundwater parameters on the column sorption was determined. Moreover, the modelling of column data using mathematical models was carried out.

MATERIALS AND METHODS

Materials

The following sorption materials: GAC, zeolite and ion-exchange resin Amberlite IR 120 H were used as column fillings.

GAC Baqua 1, purchased from Elbar-Katowice Ltd, Poland, had physicochemical characteristics as follows: BET surface area – 950–1,080 m2/g, iodine number – 900 mg/g, moisture – 5%, bulk density – 500 g/dm3, particle size – 1.0 mm.

The composition of the zeolite sample (natural zeolite in the form of clinoptilolite from tuffs of 0.5 ÷ 1.0 mm particle size) was as follows: SiO2 – 47.7%, Al2O3 – 7.3%, Fe2O3 – 20.7%, MgO – 9.4%, CaO – 9.0%, MnO – 0.3%, P2O5 – 0.2%, Na2O – 1.2%, K2O – 0.6% and TiO – 3.6%.

The ion-exchange resin Amberlite IR 120 H was purchased from Sigma-Aldrich Ltd, Poland. This resin is a gel type, strongly acidic, cation exchange resin of the sulfonated polystyrene type with particle size of 0.62–0.83 mm.

‘Synthetic groundwater’ was made up from laboratory reagents (114 mg/dm3 Zn(NO3)2·6H2O, 69 mg/dm3 Cd(NO3)2·4H2O, 83 mg/dm3 CaCl2, 339 mg/dm3 MgCl2·6H2O, 218 mg/dm3 K2SO4 and 165 mg/dm3 NaCl). After standing, the pH of the synthetic groundwater was 6.2. The initial concentrations of Zn(II) and Cd(II) were 25 mg/dm3 and the synthetic groundwater contained approximately 560 mg/dm3 of total dissolved solids. The composition of ‘synthetic groundwater’ was developed based on the analysis of groundwater samples taken from the zinc smelter site. The masses of the sorbents in columns: GAC, zeolite and resin were as follows: 11.5, 20.8 and 17.4 g.

Methods

The pH of column effluents were measured immediately after sampling with a pH/Conductivity meter (Elmetron CX-731). Solutions were filtered through 0.45 μm filters, acidified and, if necessary, kept at 4 °C and then analyzed for metals by AAS Unicam Solaar 939) or ICP MS (Elan 6000, PerkinElmer) depending on metal ions concentration. The anions concentration was measured by ion chromatography (861 Advanced Compact IC, Metrohm).

Column experiment design

Flow-through column test (using glass column, Tygon tubing, and peristaltic pump Manostat Carter) was conducted to replicate the mode of contaminant exposure within a PRB. The GAC, zeolite and ion-exchange resin were placed each in a 20 cm3 glass columns (length 250 mm, internal diameter ≈10 mm), which resulted in a pore volume of approximately 7.6, 8,4 and 9,6 cm3, respectively (the initial porosity of the medium was equaled to 0.39, 0.43 and 0.49, respectively). The column was then saturated by the upward flow of distilled water. Once saturation was achieved the water was displaced with the upward flow of the synthetic groundwater at a constant flow rate of 9.6 cm3/h. Effluent solutions were collected through a spur at the top of the columns into covered glass collection vessels and analyzed to determine the pH, metal ions (Cd, Zn, Ca, Mg, Na) and anions (nitrates, sulphates and chlorides) concentration.

Fixed-bed column data analysis

The time for breakthrough appearance and the shape of the breakthrough curve are very important characteristics for determination of the operation and the dynamic response of sorption column. The breakthrough curves show the loading behavior of metal to be removed from solution in a fixed bed and is usually expressed in terms of adsorbed metal concentration (cad = inlet metal concentration (c0) − effluent metal concentration (c)) or normalized concentration defined as the ratio of effluent metal concentration to inlet metal concentration (c/c0) as a function of time or volume of effluent for a given bed height (Aksu & Gonen 2004). The area under the breakthrough curve (A) is obtained by integrating the adsorbed concentration (cad; mg l−1) versus t (min). Plot can be used to find the total adsorbed metal quantity (maximum column capacity).

Total adsorbed metal quantity (qt; mg) in the column for a given feed concentration and flow rate is calculated from the following equation: 
formula
(1)
where Q is the flow rate (ml min−1).
Equilibrium metal uptake (qe) (or maximum capacity of the column) in the column is defined by the total amount of metal sorbed (qt) per gram of sorbent (m) at the end of total flow time: 
formula
(2)

The breakthrough is usually defined as the point when the effluent concentration from the column is about 3–5% of the influent concentration (Chen & Wang 2000).

Modelling of column data

The Adams-Bohart, Thomas and Yoon-Nelson mathematical models were used in modelling the sorption process in continuous systems in this study. These models were applied using the software Origin 2018.

Regeneration studies

The regeneration studies of loaded sorbents were carried out by upward flow of 0.1 M HCl solution at a flow rate of 2.0 cm3/min through columns.

RESULTS AND DISCUSSION

Sorption column data analysis

Adams-Bohart model

In 1920, the basic mathematical correlation that relates C/C0 and the column service time (t) for a continuous-flow system was proposed by Adams and Bohart. The model proposed by the authors assumes that the equilibrium is not instantaneous and that the sorption rate is proportional to the residual capacity of the solid and the concentration of the sorbed substance. Its equation can be described as: 
formula
(3)
in which c0 and c are the influent and effluent metal ions concentration in mg/L, kAB is the kinetic constant in L/mg min, N0 is the maximum volumetric sorption capacity in mg/L, H is the bed depth in cm, and F is the linear velocity in cm/min (Homem et al. 2018).

Thomas model

Among theories that predict the relationship between concentration and time, this model is the most commonly used model to investigate the performance of the adsorption process in a fixed bed. Developed by Thomas, this model is based on second order kinetics and considers that sorption is not limited by the chemical reaction, but controlled by the mass transfer at the interface. It can be used to describe the whole breakthrough curve, or specifically the part between the breakthrough and saturation points. The Thomas model can be expressed by Equation (4): 
formula
(4)
in which kTH is the mass transfer coefficient in mL/mg min, q0 is the equilibrium uptake capacity in mg/g, m is the mass of adsorbent packed in the column in g and Q is the flow rate in mL/min (Han et al. 2009; Homem et al. 2018).

Yoon-Nelson model

The Yoon-Nelson is based on the assumption that the rate of decrease in the probability of adsorption for each sorbate molecule is proportional to the probability of adsorbate adsorption and the probability of adsorbate breakthrough on the adsorbent. The Yoon-Nelson model not only is less complicated than other models, but also requires no detailed data concerning the characteristics of adsorbate, the type of adsorbent, and the physical properties of the adsorption bed. The Yoon-Nelson equation is expressed as: 
formula
(5)
in which kYN is the proportionality constant of the Yoon-Nelson model in min−1, and τ is the time required for 50% adsorbate breakthrough in min. The values of kYN and τ are estimated from a plot of ln versus t (Han et al. 2009; Homem et al. 2018).

Experimental and predicted breakthough curves of metal ions sorption onto reactive materials are presented in Figure 2.

Figure 2

Experimental and predicted breakthough curves of metal ions sorption using the Adams-Bohart, Thomas and Yoon-Nelson onto: (a) GAC, (b) zeolite and (c) ion-exchange resin.

Figure 2

Experimental and predicted breakthough curves of metal ions sorption using the Adams-Bohart, Thomas and Yoon-Nelson onto: (a) GAC, (b) zeolite and (c) ion-exchange resin.

As is seen in Figure 2 and Table 1 in the case of resin, breakthrough occurred for Cd(II) and Zn(II) ions after 8,750 and 12,500 min, respectively. For GAC and zeolite, the breakthroughs occurred earlier as a result of depletion of sorption capacity of these materials. Performance of GAC and zeolite PRBs remained effective (>99% metal ions removal) for the time corresponding to on average of 500 and 1,200 min, respectively. Until achieving breakthrough time, the metals concentrations have declined from 25 mg/dm3 to on average of 0.05 mg/dm3. According to WHO guidelines for drinking water quality, the cadmium permissible value is 0.003 mg/dm3. Zinc is not of health concern at levels found in drinking water; however, zinc at levels above 3 mg/dm3 may not be acceptable to consumers.

Table 1

Parameters of experimental breakthrough curves of metal ions sorption by reactive materials

Reactive material Metal ion Breakthrough time tb (min) qe (mg/g) 
Ion exchange resin Cd 8,750 1,902 
Zn 12,500 355 
Zeolite Cd 840 9.69 
Zn 1,785 75.60 
GAC Cd 535 4.66 
Zn 475 4.74 
Reactive material Metal ion Breakthrough time tb (min) qe (mg/g) 
Ion exchange resin Cd 8,750 1,902 
Zn 12,500 355 
Zeolite Cd 840 9.69 
Zn 1,785 75.60 
GAC Cd 535 4.66 
Zn 475 4.74 

Adams-Bohart, Thomas and Yoon-Nelson parameters for sorption of metal ions onto different reactive materials are presented in Table 2.

Table 2

Adams-Bohart, Thomas and Yoon-Nelson parameters for sorption of metal ions onto different reactive materials

Model Parameters Ion exchange resin
 
Zeolite
 
GAC
 
Cd Zn Cd Zn Cd Zn 
Adams-Bohart kAB (L/mg min) 0.18 × 10−5 0.18 × 10−5 2.32 × 10−5 3.36 × 10−5 2.18 × 10−5 2.26 × 10−5 
N0 (mg/L) 8,878.71 8,980.58 797.50 818.51 525.75 520.02 
R2 0.788 0.834 0.908 0.942 0.755 0.781 
Thomas kTH (mL/mg min) 0.012 0.009 0.073 0.088 0.134 0.126 
q0 (mg/g) 1,899.17 361.47 9.77 71.24 4.80 4.71 
R2 0.999 0.998 0.995 0.982 0.986 0.994 
Yoon-Nelson kYN (min−10.0003 0.0002 0.0026 0.0027 0.0034 0.0032 
τ (min) 25,475 26,792 2,340 2,694 1,334 1,240 
R2 0.993 0.985 0.957 0.924 0.915 0.966 
Model Parameters Ion exchange resin
 
Zeolite
 
GAC
 
Cd Zn Cd Zn Cd Zn 
Adams-Bohart kAB (L/mg min) 0.18 × 10−5 0.18 × 10−5 2.32 × 10−5 3.36 × 10−5 2.18 × 10−5 2.26 × 10−5 
N0 (mg/L) 8,878.71 8,980.58 797.50 818.51 525.75 520.02 
R2 0.788 0.834 0.908 0.942 0.755 0.781 
Thomas kTH (mL/mg min) 0.012 0.009 0.073 0.088 0.134 0.126 
q0 (mg/g) 1,899.17 361.47 9.77 71.24 4.80 4.71 
R2 0.999 0.998 0.995 0.982 0.986 0.994 
Yoon-Nelson kYN (min−10.0003 0.0002 0.0026 0.0027 0.0034 0.0032 
τ (min) 25,475 26,792 2,340 2,694 1,334 1,240 
R2 0.993 0.985 0.957 0.924 0.915 0.966 

As it can be seen in Table 2, the curves predicted by the Thomas model showed the best agreement with the experimental data (R2 > 0.99 in most cases). The value of sorption column capacity (qo) for resin was significantly higher compared to the value of sorption capacities for GAC and zeolite. The sorption column capacities of Cd(II) and Zn(II) ions were of 1,899 and 361 mg/g then and these values were similar to experimental values (qe). Also, the values of τ obtained from Yoon-Nelson model were very close to those obtained experimentally, which suggests that the model efficiently predicted the behaviour of the breakthrough curves in this study. The worst fitting of experimental data was obtained in the case of Adams-Bohart model, as it can be concluded from Figure 2 and the regression coefficients (R2), shown in Table 2. The obtained results confirm that this model is appropriate for analyzing only the initial part of the breakthrough curve (c/c0 = 0–0.15) (Homem et al. 2018).

A wide variety of sorbents used to remove metal ions from aqueous solutions have been reported in the literature. Table 3 presents a brief list of the published sorption capacity of various sorbents in the column system, including also the results obtained in this work. As is shown in Table 3, the sorption column capacities (qe) of Cd(II) and Zn(II) ions for ion-exchange resin Amberlite IR 120 H were significantly higher than for other sorbents reported in the literature.

Table 3

Comparison of equilibrium uptake capacity (qe) for Cd and Zn sorption in fixed-bed columns

Sorbent Equilibrium uptake capacity (mg/g)
 
Feed concentration (mg/L) Reference 
Cd Zn 
Amberlite IRC 718 119 68 600 each Malla et al. (2002)  
Green coconut shell 38 17 100 each Sousa et al. (2010)  
Waste from boron enrichment plant 86–138 80–110 150 each Atar et al. (2012)  
Citrus peels 44 20 Cd 5.62, Zn 3.27 Chatterjee & Schiewer (2014)  
GAC 0.007 0.047 1 each Sounthararajah et al. (2015)  
GAC + TNF 0.526 0.205 
Natural zeolite-rich rock 34 16 Cd 58, Zn 32 Nuić et al. (2019)  
Amberlite IR 120 H 1,902 355 25 each This study 
zeolite 9.69 75.60 
GAC 4.66 4.74 
Sorbent Equilibrium uptake capacity (mg/g)
 
Feed concentration (mg/L) Reference 
Cd Zn 
Amberlite IRC 718 119 68 600 each Malla et al. (2002)  
Green coconut shell 38 17 100 each Sousa et al. (2010)  
Waste from boron enrichment plant 86–138 80–110 150 each Atar et al. (2012)  
Citrus peels 44 20 Cd 5.62, Zn 3.27 Chatterjee & Schiewer (2014)  
GAC 0.007 0.047 1 each Sounthararajah et al. (2015)  
GAC + TNF 0.526 0.205 
Natural zeolite-rich rock 34 16 Cd 58, Zn 32 Nuić et al. (2019)  
Amberlite IR 120 H 1,902 355 25 each This study 
zeolite 9.69 75.60 
GAC 4.66 4.74 

The control of groundwater parameters during its flow through PRB is important due to the risk of porosity reduction and shortening of sorption barrier lifetime. The changes of pH and presence of competing ions could influence on metal ions sorption. Partial metals desorption may occur due to the reaction of metal ions with OH ions and precipitate as a metal hydroxides (Goher et al. 2015). Moreover, the permeability and activity of sorption materials could be impacted due to potential precipitation of groundwater constituents within a reactive barrier (Zawierucha & Malina 2012).

The changes of selected groundwater parameters during flow through sorption columns are presented in Figures 35.

Figure 3

Changes of pH of groundwater flowing through sorption columns.

Figure 3

Changes of pH of groundwater flowing through sorption columns.

Figure 4

Changes of Na concentration in groundwater flowing through sorption columns.

Figure 4

Changes of Na concentration in groundwater flowing through sorption columns.

Figure 5

Changes of NO3 concentration in groundwater flowing through sorption columns.

Figure 5

Changes of NO3 concentration in groundwater flowing through sorption columns.

The pH of the aqueous solution is an important operational parameter in the sorption process because it affects the solubility of the metal ions, concentration of the counter ions on the functional groups of the sorbent, and the degree of ionization of the sorbate during reaction (Goher et al. 2015). Figure 3 shows that the pH of groundwater has changed dramatically only as a result of flow through column filled with ion exchange resin. For GAC and zeolite, no more pH deviations from the initial value were observed. In the case of ion-exchange resin, a rapid decrease of pH from 6.2 to 2.4 is due to the release of H+ ions in ion exchange process between this material and groundwater. This decrease, which remained at a constant level until breakthrough occured, suggests high longevity and stability of ion exchange resin for the treatment of groundwater in PRB technology. When the breakthrough occurred, the pH of groundwater has gradually increased until the initial value as a result of saturation of resin bed.

The ion exchange resin could be an effective sorbent for removal of metal ions from aqueous solutions. The application of Amberlite IRC 718 resin for treatment of leachate from industrial waste landfill allowed to reduce the concentration of Cd and Zn ions from 18 to 0.1 and 1.0 mg/dm3, respectively (Fernandez et al. 2005). The effective removal of metal ions was maintained over the time corresponding to 500 resin bed volumes. Pehlivan & Altun (2006, 2007) obtained high Zn and Cd ion removal efficiency (>97%) and Pb (>87%) as a result of the using of Lewatit CNP 80 and Dowex 50 W resin, respectively. Also, the Lewatite S 100 resin (Bedoui et al. 2008) was indicated as an effective sorbent for removal (of 98%) of cadmium ions from water. The effective removal of trivalent chromium from aqueous solutions using Amberlite IRC 86 resin was also observed by Cavaco et al. (2007). On the other hand, they noted that in case of industrial effluents the removal efficiency was interfered with other ions.

In our study, simultaneous removal of sodium (Figure 4) by Amberlite IR 120 H resin did not impact on its activity for removal of heavy metals (cadmium and zinc) from groundwater. When the breakthroughs for cadmium and zinc ions occurred, the sodium cations concentration in groundwater gradually increased until inlet value. For zeolite, the initial increase of Na (as well Ca and Mg) ions concentration was observed due to ion exchange process in structure of this material (Zawierucha & Malina 2014); however, as the groundwater flows, the metal ions concentration has decreased. A similar effect was noted by Lee et al. (2010) during study of a zeolitic rock barrier for removal of zinc from water. When the breakthrough for zinc ions occurred, the desorbed cations (sodium, calcium and magnesium) concentration decreased rapidly.

For columns filled with ion-exchange resin and GAC, no major changes of concentration of co-existing Ca and Mg cations in groundwater were observed, in comparison to their inlet values.

In general, insignificant changes in anions (sulphates and chlorides) concentration (p > 0.05) suggest the lack of interactions between sorption materials and groundwater, indicating longevity and stability of these materials as the reactive barriers in groundwater remediation. Only nitrates highly interacted with GAC, as is shown in Figure 5. In this case, the decrease of NO3 concentration indicated that these anions competed in adsorption, which could be the reason of rapid depletion of GAC sorption capacity for heavy metals.

Regeneration studies

A sorbent material that not only possessed a good sorption capacity, but also showed favourable regeneration properties would contribute to a significant reduction of the overall cost of the process. Therefore, successful regeneration of the sorbent can be considered a key process for determining the applicability of a sorbent in groundwater remediation applications (Christoforidis et al. 2015).

The results of regeneration studies indicated that 0.1 M HCl solution is effective for this process and can be used as a regeneration agent. The desorption process was rapid during 100, 60 and 20 cm3 of the effluent volume for resin, zeolite and GAC, respectively; more than 98% of Cd(II) and Zn(II) ions were desorbed then.

However, a field-scale configuration of PRB should allow that saturated sorption materials can be replaced during operation, which can be achieved by using removable/replaceable ‘cassettes’ (Van Nooten et al. 2008).

CONCLUSIONS

The overall results derived from this study suggest that permeable sorption barriers can be used for effective clean-up of groundwater contaminated with heavy metals.

The ion exchange resin was the most effective sorption material of PRB. Performance of resin barrier remained effective (>99% metal ions removal) for the time corresponding to on average of about 10,000 min while times for GAC and zeolite times were on average of 500 and 1,200 min, respectively.

The high efficiency of ion-exchange resin in PRB for removal of heavy metals from groundwater was coupled with its reactivity and long barrier lifetime. The sorption capacity of the resin was significantly higher than other materials. The breakthroughs in the column tests on activated carbon and zeolite using synthetic groundwater occurred much earlier as compared to resin. Therefore, the system using resin requires smaller amount to treat a given volume of groundwater as compared to other materials. Moreover, the presence of other ions did not impact on activity and permeability of barrier filled with resin.

ACKNOWLEDGEMENTS

This work was supported by the Ministry of Science and Higher Education, Poland under grant number NN 525394139.

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