Qin Li,
Daoping Peng*,
Zheng Wu and
Tao Huang
School of Geosciences and Environmental Engineering, Southwest Jiaotong University, Chengdu, China. E-mail: pdp0330@swjtu.cn
First published on 17th December 2020
Three commercially available bentonite–polymer composite geosynthetic clay liners (BPC GCLs) were selected for hydraulic conductivity testing, respectively permeated by two types of bauxite leachates with high alkalinity (pH > 12) and high ionic strength (620.3 mM). The influence of BPC GCLs on the attenuation behavior of Cr/Pb in the bauxite leachates was analyzed. The BPC GCLs with a low hydraulic conductivity (k < 10−10 m s−1) retard the migration of Cr and Pb and the Cr had a higher mobility than Pb in the BPC GCLs. Scanning electron microscope (SEM) microstructure analysis showed that the migration and attenuation behavior of Cr/Pb mainly depended on the chemical properties of the leachates, polymer content and the microstructure of the polymer. Higher attenuation of heavy metals was obtained with bauxite leachates having higher ionic strength. Sufficient polymer content is needed to ensure BPC GCLs have adequately low hydraulic conductivity to suppress attenuation of heavy metals. The gelatinous structure associated with hydrated linear or crosslinked polymer diminishes when the polymer in a BPC is in contact with bauxite leachates. Compromising the hydrogel structure promotes polymer elution and leaves pore space open, resulting in attenuation of heavy metals.
Geosynthetic clay liners (GCLs) with strong adsorption and low permeability have been widely used in red mud storage according to the environmental protection and anti-seepage requirements.15–18 GCLs are geosynthetic materials made of two layers of geotextile (woven or non-woven) with a layer of 5–10 mm thick natural sodium-based bentonite, which are knitted and reinforced.19,20 The main component of sodium-based bentonite is sodium-based montmorillonite,21 which produces osmotic expansion through strong water absorption of sodium ions, reduces seepage pores and increases curvature.22,23 However, extreme pH conditions, cation exchange, and high ionic strength solutions could cause sodium-based montmorillonite to lose its permeability.24,25
In order to improve the chemical permeability of conventional sodium bentonite GCLs, bentonite–polymer composite GCLs (BPC GCLs) have been developed in recent years.26–28 The research of hyperbranched poly(amidoamine) (PAMAM) as a continuous phase using aqueous dispersion method showed that intercalation of PAMAM took place in pre-expanded kaolinite to give exfoliated nanocomposite.29 The modified montmorillonite by the preparation of poly (methylmethacrylate) nanocomposites with basal distance 1.95 nm exhibited better thermal stability and revealed tremendous affinity for removing pesticides from aquatic solutions.30 The prepared of polyaniline/montmorillonite nanocomposites by intercalating the emulsion of aniline monomer with treated organically layers using ammonium peroxydisulfate as an initiator showed an enhancement in the conductivity values.31
The modified bentonite GCLs use polymer (such as sodium carboxymethyl cellulose) as an additive to modify sodium bentonite which make it resistant to harsh chemical environments.32,33 A large number of studies have shown the characterized behaviour of BPC GCLs to coal combustion product leachate (pH = 8.5, I = 39.5 mM), trona leachate (pH = 11, I = 1.05 M) and bauxite leachate (pH = 13, I = 2.35 M), but the attenuation of heavy metals has received little attention.15,28 The attenuation of heavy metals in BPC GCLs is mainly attributed to the adsorption on clays, especially under different environmental conditions.34 Studies on the migration of zinc oxide nanoparticles (nZnO) in geosynthetic clay liners (GCLs) have found that the migration of metals has a great relationship with osmotic pressure. As the pressure increases, the pores of the GCL are compressed and the attenuation of nZnO is greatly reduced.35 Through long-term prediction research on the reduction of heavy metals by GCLs, it is found that GCLs can effectively delay the breakthrough times of heavy metals, especially the attenuation of heavy metals Fe and Mn adsorbed on the bentonite showed regularity.36 However, the attenuation mechanism, especially the material analysis method using microscopic imaging, has not been thoroughly understood.
The purpose of this study is to explore the mechanism that control the attenuation of the heavy metals of BPC GCLs. Hydraulic conductivity tests were conducted on commercially available BPC GCLs using two characteristic Chinese bauxite leachates and the attenuation of different heavy metals is evaluated. Micro-scale image analysis of specimens obtained by scanning electron microscopy (SEM) was used to understand mechanisms controlling the attenuation of the heavy metals permeated with bauxite leachates.
Bentonite mineralogy, physical properties, and polymer content of the GCLs are showed in Table 1. Each BPC GCL comprised sand-sized bentonite granules with a median particle size (D50) between 0.7 mm and 0.9 mm. Clay minerals and bulk minerals on the bentonite were quantified using Quantitative X-ray diffraction (XRD).38 The bentonite contained 67% to 85% montmorillonite, and measurable quartz, feldspar, illite, calcite, kaolinite, potassium feldspar. Polymer content of BPC GCLs was measured based on loss on ignition (LOI).39
Property | Geosynthetic clay liner | ||
---|---|---|---|
CP6.5 | CP7.5 | CP10.8 | |
Bentonite mass per unit area (kg m−2) | 3.6 | 3.7 | 3.6 |
Initial thickness (mm) | 6.4–7.4 | 5.9–6.7 | 6.5–7.3 |
Initial water content (%) | 4.4 | 4.8 | 5.6 |
Median granule size (mm) | 0.8 | 0.7 | 0.9 |
Montmorillonite content (%) | 76 | 67 | 85 |
Loss on ignition (%) | 8.0 ± 0.5 | 9.0 ± 0.3 | 12.2 ± 0.4 |
Polymer content (%) | 6.5 ± 0.5 | 7.5 ± 0.3 | 10.8 ± 0.4 |
Leachate samples | GX | SD |
---|---|---|
Chemical parameters | ||
pH | 12.1 | 12.6 |
EC @ 25 °C (S m−1) | 0.97 | 5.11 |
ORP (mV) | −46.0 | −110.0 |
Ionic strength (mM) | 224.5 | 620.3 |
RMD (M1/2) | 0.03 | 2.6 |
Major elements and anions | ||
Al (mg L−1) | 1095.5 | 745.5 |
Ca (mg L−1) | 88.9 | 57.1 |
Na (mg L−1) | 3506.0 | 10650.0 |
Mg (mg L−1) | 15.0 | 10.5 |
K (mg L−1) | 239.3 | 81.8 |
Si (mg L−1) | 41.7 | 89.9 |
Cl− (mg L−1) | 877.1 | 6490.5 |
F− (mg L−1) | 49.8 | 121.8 |
SO42− (mg L−1) | 741.7 | 7453.3 |
Heavy metals | ||
Cr (mg L−1) | 0.1 | 5.9 |
Pb (mg L−1) | 0.3 | 1.1 |
The pH, EC, and oxidation–reduction potential (ORP) of bauxite leachates were evaluated with accumet XL50 bench-top meters (Fisher Scientific, Hanover Park, IL). The bauxite leachates are hyperalkaline, with pH ranging from 11.3 to 13.2. The ionic strength ranges from 77.3 mM to 620.3 mM. EC of the bauxite leachates ranges from 0.44 to 5.11 S m−1 at 25 °C. The ORP ranges from −110.0 to −63.0 mV which indicated a reducing condition.
The concentrations of major elements (Na, K, Ca, Mg, Al, and Si) and heavy metals (Cr and Pb) of the bauxite leachates, the influent, and the effluent were evaluated by inductively coupled plasma mass spectrometry (ICP-MS, Agilent Technologies 700 Series, Santa Clara, CA, USA). The anions of the bauxite leachates, including chloride (Cl−), fluoride (F−), and sulfate (SO42−), were conducted by ion chromatography (IC, Shimadzu HIC-SP, Kyoto, Japan).The major elements of the bauxite leachates are Al (152–1090 mg L−1) and Na (1200–41300 mg L−1) and the major anions are Cl− (150–6590 mg L−1) and SO42− (162–7450 mg L−1).
The specimens of BPC GCLs were hydrated with permeant liquids for 48 h in the flexible-wall permeameters which were assembled at an effective stress of 20 kPa and hydraulic gradient of 0. Hydraulic conductivity tests continued until termination criteria was reached. The hydraulic equilibrium and chemical equilibrium of termination criteria generally were satisfied between BPC GCLs and permeant liquids:41,42 (1) the ratio of incremental outflow to inflow (Qout/Qin) was within 1 ± 0.25, (2) the pH and electrical conductivity (EC) of the effluent were within 10% of the influent, pHout/pHin and ECout/ECin were within 1 ± 0.1 (3) the concentrations of major cations (i.e., Na+, K+, Ca2+, and Mg2+) of the effluent were within 10% of the influent.
GCL | Permeant liquid | Hydraulic conductivity (m s−1) | Swell index (mL/2 g) | CCr/CCro = 1 (mL) | CPb/CPbo = 1 (mL) |
---|---|---|---|---|---|
CP 6.5 | DI water | 1.7 × 10−13 | 29.0 | — | — |
GX | 3.1 × 10−11 | 18.0 | 2380 | 2100 | |
SD | 5.0 × 10−9 | 8.2 | 1500 | 1660 | |
CP 7.5 | DI water | 3.3 × 10−12 | 28.0 | — | — |
GX | 7.2 × 10−11 | 16.0 | 2520 | 2430 | |
SD | 6.7 × 10−11 | 6.5 | 1800 | 1880 | |
CP 10.8 | DI water | 9.6 × 10−12 | 28.0 | — | — |
GX | 3.2 × 10−11 | 17.0 | 2700 | 2560 | |
SD | 6.6 × 10−12 | 5.9 | 1900 | 2140 |
Fig. 1 The ratio of the inflow and effluent concentrations for (a) Cr (i.e., CCr/CCro) and (b) Pb (i.e., CPb/CPbo) in the hydraulic conductivity tests to the SD and GX bauxite leachates. |
It can be clearly seen from Table 3 and Fig. 1 that as the number of polymers increases, the hydraulic conductivity gradually decreases and the breakthrough time of Cr/Pb is delayed accordingly. Moreover, the breakthrough time of SD bauxite leachates with the highest ionic strength was significantly earlier than that of GX bauxite leachates with low ionic strength. The ratios of CCr/CCro and CPb/CPbo increase systematically as the permeation continuous. The Cr breakthrough (i.e., CCr/CCro = 1) for the CP6.5 GCL occurred at a 1500 mL cumulative inflow when permeated with the SD bauxite leachates. The breakthrough of Cr is likely due to the high hydraulic conductivity of the CP6.5 GCL to SD (5.0 × 10−9 m s−1), and the migration of Cr is likely controlled from advection. In the early stage, the breakthroughs of Cr and Pb for the tests with low hydraulic conductivities (<10−10 m s−1) were not evident during the current testing period (>1000 mL cumulative inflow or >10 PVFs). After a long period of testing (cumulative flow > 2000 mL or >20 PVFs), the breakthrough of Cr and Pb in the test of low hydraulic conductivity (<10−10 m s−1) becomes obvious and the maximum CCr/CCro reaches approximately 1. Comparing the C/Co for Cr and Pb, the Cr has a higher mobility than Pb, which is likely due to the formation of the highly soluble oxyanion (i.e., CrO42−) when under alkaline conditions.
The osmotic expansion of bentonite in BPC GCLs is another major factor contributing to the attenuation of heavy metals. Swell index of the bentonite BPC GCLs is shown in Fig. 2 as a function of bauxite leachates. The attenuation of heavy metals is closely related to the swell index of bentonite, which indicates that the osmotic mechanism of bentonite controls the attenuation of heavy metals. As the swell index increases, the hydraulic conductivity becomes smaller, which lead to smaller penetration and slower attenuation of heavy metals. For example, the swell index for the CP6.5 of BPC GCLs decreases with increasing bauxite leachates concentration (Table 3) from approximately 29 mL = 2 g in DI water to 8.2 mL = 2 g in SD bauxite leachates and correspondingly the hydraulic conductivity is 1.7 × 10−13 m s−1 to DI water and 1.7 × 10−9 m s−1 for SD bauxite leachates with higher ionic strength. The time of breakthrough Cr increased from 1500 mL to 2380 mL with increasing the swell index in SD and GX bauxite leachates. Similarly, the time of breakthrough Pb was earlier for SD bauxite leachates with higher ionic strength than GX bauxite leachates.
SEM images permeated with DI water and bauxite leachates illustrate how osmotic expansion of bentonite affects the attenuation of heavy metals (Fig. 3). Fig. 3(a) shows the microstructure of the SEM about the sodium-based bentonite permeated with DI water. The montmorillonite mineral layer in the bentonite could occur osmotic expansion and absorb a large amount of water, which result very low hydraulic conductivity of bentonite. The osmotic expansion reduces the porosity and the fluid velocity and bends the fluid flow path.43,44 Fig. 3(b) shows the microstructure of the SEM about the sodium-based bentonite permeated with GX bauxite leachates with a higher ionic strength of 224.5 mM. The montmorillonite mineral layer in the bentonite could occur smaller osmotic expansion, which result larger hydraulic conductivity under GX bauxite leachates. As the increase of ionic strength and decrease of swell index, smaller osmotic expansion and larger porosity occurred. Similarly, Fig. 3(c) shows the microstructure of SEM about the sodium-based bentonite permeated with SD bauxite leachates with a highest ionic strength of 620.3 mM. It could be clearly seen that the microstructure of bentonite has undergone more obvious porosity and the time of breakthrough Cr/Pb increased sharply.
Fig. 4 SEM images of bentonite–polymer from BPC GCLs in DI water: (a) linear polymer structure (CP6.5) and (b) crosslinked polymer structure (CP7.5). |
Enough polymer could block the pore spaces between the bentonite granules and retard attenuation of heavy metals by suppressing osmotic expansion of bentonite.37 Hydraulic conductivity of the BPC GCLs to the bauxite liquors is shown in Fig. 5 as a function of polymer loading. With more polymer, the porosity will be correspondingly smaller and the rate of attenuation of heavy metals will be slower. For example, the polymer loading for the BPC GCLs increases from approximately 6.5%, 7.5% to 10.8%, the hydraulic conductivity is 5.0 × 10−9 m s−1, to 6.7 × 10−11 m s−1 and 6.6 × 10−12 m s−1 for SD bauxite leachates with higher ionic strength. The time of breakthrough Cr increased from 1500 mL to 1800 mL and 1900 mL with increasing polymer loading.
With polymer elution occurring, the attenuation of heavy metals increased and the breakthrough occurred. Polymer elution indicated the pore spaces opened up and heavy metals eluted. At the same time, the concentration of leachates increases, the more polymer flows out with time, and the shorter the time for heavy metal breakthrough. For example, the time of breakthrough Cr/Pb were earlier for SD bauxite leachates with higher ionic strength than GX bauxite leachates. These finding showed that polymer content was necessary to block the pore spaces and maintain the content of heavy metals in bauxite leachates.
(1) The BPC GCLs had hydraulic conductivities to bauxite leachates ranging from 10−8 to 10−12 m s−1, and the concentrations of Cr (Pb) in the SD and GX bauxite leachates are 5.9 (1.1) and 0.1 (0.3) mg L−1, respectively. Meanwhile, the BPC GCLs with a low hydraulic conductivity (k < 10−10 m s−1) retard the migration of Cr and Pb and the breakthroughs of Cr and Pb were not evident for the BPC GCLs with low hydraulic conductivities (k < 10−10 m s−1). After a long period of testing (cumulative flow > 2000 mL or >20 PVFs), the breakthrough of Cr and Pb in the test of low hydraulic conductivity (<10−10 m s−1) becomes obvious and the maximum CCr/CCro reaches approximately 1. The Cr had a higher mobility than Pb in the BPC GCLs.
(2) The attenuation of heavy metals in bauxite leachates depends on the chemical properties of the liquor, the adsorption and osmotic expansion of bentonite, the polymer content and microstructure. Higher attenuation of heavy metals was obtained with bauxite leachates having higher ionic strength. The time of breakthrough Cr increased from 1500 mL to 2380 mL with increasing the swell index in SD and GX bauxite leachates. Similarly, the time of breakthrough Pb was earlier for SD bauxite leachates with higher ionic strength than GX bauxite leachates.
(3) Sufficient polymer content is needed to ensure BPC GCLs have adequately low hydraulic conductivity to suppress attenuation of heavy metals. The gelatinous structure associated with hydrated linear or crosslinked polymer diminishes when the polymer in a BPC is contacted by bauxite leachates. Compromising the hydrogel structure promotes polymer elution and leaves pore space open, resulting in attenuation of heavy metals. The polymer loading for the BPC GCLs increases from approximately 6.5%, 7.5% to 10.8%, the hydraulic conductivity is 5.0 × 10−9 m s−1, to 6.7 × 10−11 m s−1 and 6.6 × 10−12 m s−1 for SD bauxite leachates with higher ionic strength. The time of breakthrough Cr increased from 1500 mL to 1800 mL and 1900 mL with increasing polymer loading.
This journal is © The Royal Society of Chemistry 2020 |