Fluoride Action Network

Volcanic Rock Materials for Defluoridation of Water in Fixed-Bed Column Systems

Source: Molecules 26(4),977. | Authors: Geleta WS, Alemayehu E, Lennartz B.
Posted on February 12th, 2021
Industry type: Water Treatment


Consumption of drinking water with a high concentration of fluoride (>1.5 mg/L) causes detrimental health problems and is a challenging issue in various regions around the globe. In this study, a continuous fixed-bed column adsorption system was employed for defluoridation of water using volcanic rocks, virgin pumice (VPum) and virgin scoria (VSco), as adsorbents. The XRD, SEM, FTIR, BET, XRF, ICP-OES, and pH Point of Zero Charges (pHPZC) analysis were performed for both adsorbents to elucidate the adsorption mechanisms and the suitability for fluoride removal. The effects of particle size of adsorbents, solution pH, and flow rate on the adsorption performance of the column were assessed at room temperature, constant initial concentration, and bed depth. The maximum removal capacity of 110 mg/kg for VPum and 22 mg/kg for VSco were achieved at particle sizes of 0.075–0.425 mm and <0.075 mm, respectively, at a low solution pH (2.00) and flow rate (1.25 mL/min). The fluoride breakthrough occurred late and the treated water volume was higher at a low pH and flow rate for both adsorbents. The Thomas and Adams–Bohart models were utilized and fitted well with the experimental kinetic data and the entire breakthrough curves for both adsorbents. Overall, the results revealed that the developed column is effective in handling water containing excess fluoride. Additional testing of the adsorbents including regeneration options is, however, required to confirm that the defluoridation of groundwater employing volcanic rocks is a safe and sustainable method.

1. Introduction

Credible evidence from scientific literature substantiates both beneficial and detrimental effects of fluoride on human health with only a narrow range between intake associated with these effects [1,2]. Consumptions of fluoride in low concentrations (<1.0 mg/L) is an essential micronutrient for the healthy development of bone and dental enamel [3]; however, it leads to the development of fluorosis if it is consumed beyond the permissible limit (>1.5 mg/L) [4].

In many parts of the world, groundwater sources are the single largest supply of drinking water. For many rift communities, it may be the only economically viable option for drinking water. In the Ethiopian rift valley, about 40% of deep and shallow wells are contaminated with up to 26 mg/L of fluoride [5,6]. The weathering of primary rocks and leaching of fluoride-containing minerals in soils yield fluoride-rich groundwater in the Ethiopian Rift, which is generally associated with a low calcium content and high bicarbonate concentrations [7,8].

Globally, more than 200 million people, including Ethiopia, rely on groundwater with a fluoride concentration above the permissible level [3,4,9]. According to the Central Statistical Agency of Ethiopia report [10], 3.8% of the population is affected by high-level fluoride concentrations (>1.5 mg/L) in groundwater, which is used for drinking purposes. In general, fluorosis turns out to be the most widespread geochemical-based disease in the East African rift, affecting more than 80 million people [11,12,13,14]. Thus, due to the health effect of high fluoride in groundwater, it is essential to reduce excess fluoride concentrations to the allowable limit (<1.5 mg/L).

So far, various technologies such as coagulation/precipitation, electro-coagulation, membrane separations, ion exchange, and adsorption had been attempted for efficient defluoridation of groundwater [15,16,17,18]. Some of the shortfalls of these techniques include expensiveness, fouling issues, regular maintenance, and complicated operational procedures. In comparison to the techniques mentioned above, the adsorption methodology is still one of the most widely applied methods, taking the lead of high removal efficiency, cost-effectiveness, ease of operation, simplicity of design, and availability of large varieties of adsorbents [19,20].

Various adsorbents have been investigated and reported for the removal of excess fluoride from water in an effective manner. Some of the widely employed adsorbents are La (III)-Al (III)-activated carbon modified by chemical route [21], biomaterial functionalized cerium nanocomposite [22], Quaternized Palm Kernel Shell (QPKS) [23], bone char and activated alumina [24], bone char [25], renewable biowaste [26], MgFe2O4–chitosan–CaAl nanohybrid [27], carbon nanotube composite [15], Neem Oil-Phenolic Resin Treated Bio-sorbent [17], etc. However, many of these suffer from either time-consuming synthesis procedure, high processing costs, availability of raw materials, or short lifespan, which makes them impractical to be applied in the rift valleys that are essentially impacted by high fluoride concentration in water [1]. Consequently, efforts have been made to obtain easily accessible and long-lasting, low-cost, and efficient adsorbents that may be applied for the purification of water in low-income countries such as Ethiopia.

In recent years, volcanic rocks (VPum and VSco) have received significant interest for pollutant removal due to their valuable properties such as high surface area, low-cost, easy accessibility, good mechanical resistance, and availability in large quantities [28]. The source of these rocks is volcanic magma that formed during volcanic eruptions. Pumice (VPum) is a finely porous rock frothy with air bubbles; Scoria (VSco) is a rough rock that seems like furnace slag [28]. VPum is often formed from rhyolite magma [28], it can also develop from trachytic or dacitic magma. Due to its high porosity and low specific gravity, it has been used for water and wastewater treatment processes [29]. VSco is a vesicular pyroclastic rock with basaltic compositions, reddish-brown to black, denser than VPum, somewhat porous with high surface area and strength. Both volcanic rocks are found in abundance in Europe (Italy, etc.), Central America, Southeast Asia (Indonesia, etc.), and East Africa (Ethiopia, Eritrea, etc.) [28,29]. Although several studies have been conducted on the application of volcanic rocks for pollutants-laden wastewaters [28,29,30,31], very little research has been directed to the defluoridation of groundwater using volcanic rocks.

Previously, defluoridation research has been conducted on batch experiments using natural adsorbents [6,32]. The sorption capacity of adsorbents gained from batch equilibrium is valuable in giving basic information about the effectiveness of the adsorbents. Nevertheless, the data obtained from batch studies may not be appropriate for continuous processes where the contact time for the achievement of an equilibrium might be insufficient [33]. Consequently, studies by different authors [34,35,36] reveal that continuous processes mode (fixed-bed column set-up) yields reliable information about the breakthrough time, appropriate adsorption conditions, and the stability of the adsorption performance which can then be used to evaluate the potential of prepared adsorbents for industrial applications [1]. Therefore, there is an interest to conduct adsorption studies in a flow-through system.

The primary objectives of the current work were to (i) investigate the fluoride sorption capacity of VPum and VSco in fixed-bed column set-up, (ii) compare the adsorption properties of both adsorbents with each other, (iii) assess the fluoride adsorption mechanisms with respect to varying solution pH, adsorbent particle size, and flow rate, (iv) deeper analyze the adsorption processes employing mathematical models such as the Adams–Bohart and Thomas model, and (v) finally verify the suitability of the models for the design of flow-through systems for the removal of fluoride from aqueous solutions.

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