Long-term treatment of acid mine drainage by alkali diffusion ceramic reactor: Simultaneous metal removal mechanisms.

A novel alkali diffusion reactor using ceramic porous media (ceram-ADR) was designed for the long-term remediation of acid mine drainage (AMD) without external energy. The filling material was newly applied to improve the ceram-ADR for intensive long-term treatment of acidity and metals in AMD. Activated carbon (AC), polyurethane (PU), or MgO-incorporated polyurethane (PU-MgO) were inserted as filling materials into ceram-ADR. NaHCO3 was used as the alkaline chemical. PU did not enhance the neutralizing capacity of ADR and metal removal efficiency. Although the ceram-ADR with PU-MgO showed long-term removal efficiency for all metals up to 545 bed volumes (BVs), the effluent pH complied with the mineral mining and processing effluent guidelines during 45 BVs. Ceram-ADR with AC enhanced the long-term treatment (up to a year) of metals and acidity in AMD. Mn concentration in the effluent discharged from ceram-ADR exceeded the mineral mining and processing effluent guidelines, followed by Zn, Al, and Fe. The main removal mechanism for metals was precipitation as a metal hydroxide or metal carbonate. The ion exchange of metal ions on the surface of ceramic porous media and AC can influence the adsorption behavior, which is responsible for 15.3% of the total removal of metals. The ceram-ADR with AC could be reused at least five times with no appreciable loss in activity. These results highlight the hybrid operation of ADR for the best performance in mining areas where the passive and active system are insufficient because of low efficiency, budget limitations, and geological sites.

Mechanism of simultaneous removal of aluminum and fluoride from aqueous solution by La/Mg/Si-activated carbon.

La/Mg/Si-activated carbon derived from palm shell has been a suitable material for removal of aluminum and fluoride from aqueous solution. In the study, the mechanism of simultaneous removal of aluminum and fluoride by La/Mg/Si-activated carbon (La/Mg/Si-AC) was investigated to understand its high efficiency. It was found that the removal of aluminum and fluoride by La/Mg/Si-AC was favored at lower pH compared to the point of zero charge of La/Mg/Si-AC and high temperature. Adsorption capacity of Al(OH)4- was about 10 times higher than that of F- due to the strong binding affinity of Al(OH)4- on protonated surface and competition between F- and OH- toward charged adsorption site. Kinetics results showed that the aluminum and fluoride adsorption were explained using the pseudo-second-order kinetic model and intra-particle diffusion model. Adsorption process of Al(OH)4- and F- was driven by the potential rate-limiting step involved in mass transport process occurred on the boundary diffusion layer of porous adsorbent surface. Electrostatic interaction between protonated surface of La/Mg/Si-AC and negatively charged ions (i.e., Al(OH)4- and F-) as well as ion-exchange between hydroxide and ionic metal species were important mechanisms in the process of aluminum and fluoride adsorption. Driving forces for adsorption of individual Al(OH)4- and F- were not entirely different. Identifying the dominant mechanism will be helpful in understanding the adsorption process and developing new adsorbent.

Enhanced adsorption of bisphenol A and sulfamethoxazole by a novel magnetic CuZnFe2O4-biochar composite.

The widespread occurrence of endocrine-disrupting compound and pharmaceutical active compounds such as bisphenol A (BPA) and sulfamethoxazole (SMX) in natural freshwater resources can cause serious environmental problems even at low exposure levels. In this work, in order to remove BPA and SMX from aqueous solutions, a novel biochar-supported magnetic CuZnFe2O4 composite (CZF-biochar) was synthesized by a facile one-pot hydrothermal process. After characterization studies, the key factors affecting BPA and SMX adsorption on CZF-biochar were comprehensively investigated. The primary mechanisms for BPA and SMX adsorption included charge-assisted H-bonding, hydrophobic, and π-π electron donor-acceptor interactions. In summary, considering the fast kinetics, high adsorption properties, easy magnetic separation, and recyclability for multiple reuses, the CZF-biochar composite has potential for the removal of BPA, SMX, and potentially other emerging organic contaminants from contaminated soil and water.

Sonophotocatalytic degradation of bisphenol A and its intermediates with graphitic carbon nitride.

Since bisphenol A (BPA) exhibits endocrine disrupting action and high toxicity in aqueous system, there are high demands to remove it completely. In this study, the BPA removal by sonophotocatalysis coupled with nano-structured graphitic carbon nitride (g-C3N4, GCN) was conducted with various batch tests using energy-based advanced oxidation process (AOP) based on ultrasound (US) and visible light (Vis-L). Results of batch tests indicated that GCN-based sonophotocatalysis (Vis-L/US) had higher rate constants than other AOPs and especially two times higher degradation rate than TiO2-based Vis-L/US. This result infers that GCN is effective in the catalytic activity in Vis-L/US since its surface can be activated by Vis-L to transport electrons from valence band (VB) for utilizing holes (h+VB) in the removal of BPA. In addition, US irradiation exfoliated the GCN effectively. The formation of BPA intermediates was investigated in detail by using high-performance liquid chromatography-mass spectrometry (HPLC/MS). The possible degradation pathway of BPA was proposed.

Fabrication of graphene-oxide/ß-Bi2O3/TiO2/Bi2Ti2O7 heterojuncted nanocomposite and its sonocatalytic degradation for selected pharmaceuticals.

A graphene-oxide (GO)/ß-Bi2O3/TiO2/Bi2Ti2O7 heterojuncted nanocomposite, designated as GBT, was synthesized via a two-step hydrothermal process. The sonocatalytic activity of the GBT was evaluated at several frequencies (28, 580, and 970 kHz) and compared with Bi-doped GO (GB) and Ti-doped GO (GT). Transmission electron microscopy images showed heterojuncted crystal structures of Bi and Ti on GO, and X-ray diffraction patterns verified that the crystal structures consisted of ß-Bi2O3, TiO2, and Bi2Ti2O7 nanocomposites. Energy-dispersive X-ray spectroscopy revealed a higher proportion of metal on GBT surfaces compared with GB and GT surfaces. The energy band gaps of GT, GB, and GBT were 3.0, 2.8, and 2.5 eV, respectively. Two pharmaceuticals (PhACs; carbamazepine [CBZ] and acetaminophen [ACE]) were selected and treated under sonolytic conditions at frequencies of 28, 580, and 970 kHz at a power level of 180 W L-1. The selected pharmaceuticals, present at initial concentrations of 20 µM, were reduced by over 99% by ultrasonic irradiation in the presence of GBT. The 580 kHz treatment achieved the most rapid organic removal among the frequencies tested. The removal kinetic of CBZ was higher than that of ACE owing to its relatively high hydrophobicity. High sonocatalytic activity of GBT was observed through measurement of H2O2 in solution. Because of its low band gaps and high surface activity, GBT exhibited higher sonolytic activity in removing selected PhACs than GT or GB.

Sonocatalytic degradation of carbamazepine and diclofenac in the presence of graphene oxides in aqueous solution.

This research investigated the removal of carbamazepine (CBZ) and diclofenac (DCF) in water using ultrasonic (US) treatment in the absence or presence of graphene oxides (GOs). Three frequencies and three pH conditions were tested (28, 580, and 1000 kHz and 3.5, 7, and 9.5, respectively). Regarding the effects of US frequency and pH, 580 kHz and pH 3.5 were more effective at removing CBZ and DCF (>86% for CBZ and >92% for DCF) than 1000/28 kHz and pH 7/9.5 within 60 min. However, sonocatalytic removal was enhanced in the presence of GOs; more than 99% CBZ and DCF removal was achieved at 580 kHz and pH 3.5 within 40 min. The sonicated GOs were more stable at 28 kHz than at higher frequencies of 580 and 10,00 kHz. The adsorption of CBZ and DCF has increased when GOs were sonicated at 28 kHz (44% and 61%, respectively) compared with 580 kHz (34% and 52%, respectively) and 1000 kHz (18% and 39%, respectively). The negative charges of GOs increased at 28 kHz (-105.1 mV), however, it decreased at higher frequencies such as 580 kHz (-71.5 mV) and 1000 kHz (-58.6 mV), which led to increased electrostatic repulsion that increased the stability of the GO particles in water. The overall enhancement in CBZ and DCF removal was due to an increase in cavitational bubbles, which in turn led to increased production of OH• and enhanced adsorption due to dispersion (resulting from US irradiation), which caused an increase in active adsorption sites of the GOs.

Sonocatalytic activity of a heterostructured ß-Bi2O3/Bi2O2CO3 nanoplate in degradation of bisphenol A.

Novel heterostructured ß-Bi2O3/Bi2O2CO3 nanoplates (hBN) were synthesized to observe the sonocatalytic degradation of bisphenol A (BPA) (widely used as a model pollutant) under ultrasonic (US) irradiation. Prior to obtaining the hBN, the Bi2O2CO3 micropowder precursor was prepared under hydrothermal conditions and then converted to hBN by increasing the calcination temperature to 300 °C. The synthesized hBN samples were characterized by field emission scanning electron microscope with energy dispersive X-ray analysis (FESEM/EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), ultraviolet-visible spectrophotometer diffuse reflection spectroscopy (UV-vis DRS), and X-ray photoelectron spectroscopy (XPS). The hBN/US system exhibited greater sonocatalytic activity for the degradation of BPA than the US treatment with the single element bismuth oxide, ß-Bi2O3 prepared by annealing the Bi2O2CO3 precursor at 400 °C for 1 h. The US frequency and US power intensity in the hBN/US system were the key operating parameters, which were responsible for the complete degradation of BPA during 6 h of reactions. The degradation efficiency of BPA under the US irradiation was positively correlated with the dose of hBN. Our findings indicate that heterostructured hBN can be used as an efficient sonocatalyst for the catalytic degradation of BPA in water and wastewater treatment.

Titanium dioxide-based sonophotocatalytic mineralization of bisphenol A and its intermediates.

In this study, bisphenol A (BPA) removal by sonophotocatalysis coupled with commercially available titanium dioxide (TiO2, P25) was assessed in batch tests using energy-based advanced oxidation combining ultrasound (US) and ultraviolet (UV). The kinetics of BPA removal were systematically evaluated by changing operational parameters, such as US frequency and power, mechanical stirring speed, and temperature, but also comparison of single and coupled systems under the optimum US conditions (35 kHz, 50 W, 300 rpm stirring speed, and 20 °C). The combination of US/UV/P25 exhibited the highest BPA removal rate (28.0 × 10-3 min-1). In terms of the synergy index, the synergistic effect of sonophotocatalysis was found to be 2.2. This indicated that sonophotocatalysis has a considerably higher removal efficiency than sonocatalysis or photocatalysis. The removal of BPA was further investigated to identify BPA byproducts and intermediates using high-performance liquid chromatography-mass spectrometry. Five main intermediates were formed during sonophotocatalytic degradation, and complete removal of BPA and its intermediates was obtained after 3 h of operation. The degradation pathway of BPA by sonophotocatalysis was also elucidated.

An efficient and economical treatment for batik textile wastewater containing high levels of silicate and organic pollutants using a sequential process of acidification, magnesium oxide, and palm shell-based activated carbon application.

Considering the chemical properties of batik effluents, an efficient and economical treatment process was established to treat batik wastewater containing not only high levels of Si and chemical oxygen demand (COD), but also toxic heavy metals. After mixing the effluents obtained from the boiling and soaking steps in the batik process, acidification using concentrated hydrochloric acid (conc. HCl) was conducted to polymerize the silicate under acidic conditions. Consequently, sludge was produced and floated. XRD and FT-IR analyses showed that wax molecules were coordinated by hydrogen bonding with silica (SiO2). The acidification process removed ∼78-95% of COD and ∼45-50% of Si, depending on the pH. In the next stage, magnesium oxide (MgO) was applied to remove heavy metals completely and almost 90% of the Si in the liquid phase. During this step, about 70% of COD was removed in the hydrogel that arose as a consequence of the crosslinking characteristics of the formed nano-composite, such as magnesium silicate or montmorillonite. The hydrogel was composed mainly of waxes with polymeric properties. Then, the remaining Si (∼300 mg/L) in the wastewater combined with the effluents from the rinsing steps was further treated using 50 mg/L MgO. As a final step, palm-shell activated carbon (PSAC) was used to remove the remaining COD to < 50 mg/L at pH 3. Overall, the sequential process of acidification and MgO/PSAC application developed could serve as an economical and effective treatment option for treating heavily polluted batik effluents.

Comparative effectiveness of mixed organic substrates to mushroom compost for treatment of mine drainage in passive bioreactors.

Bioreactors are one possible best sustainable technology to address the mine-impacted water problems. Several prospective substrates (mushroom compost, cow manure, sawdust, wood chips, and cut rice straw) were characterized for their ability to serve as a source of food and energy for sulfate-reducing bacteria. Twenty bench-scale batch bioreactors were then designed and set up to investigate relative effectiveness of various mixtures of substrates to that of mushroom compost, the most commonly used substrate in field bioreactors, for treating mine drainage with acidic (pH 3) and moderate pH (pH 6). Overall, reactive mixtures showed satisfactory performances in generating alkalinity, reducing sulfate and removing metals (Al>Fe>Mn) (up to 100%) at both pH conditions, for all substrates. The mixture of sawdust and cow manure was found as the most effective whereas the mixture containing 40% cut rice straw gave limited efficiency, suggesting organic carbon released from this substrate is not readily available for biodegradation under anaerobic conditions. The mushroom compost-based bioreactors released significant amount of sulfate, which may raise a more concern upon the start-up of field-scale bioreactors. The correlation between the extent of sulfate reduction and dissolved organic carbon/SO(4)(2-) ratio was weak and this indicates that the type of dissolved organic carbon plays a more important role in sulfate reduction than the absolute concentration and that the ratio is not sensitive enough to properly describe the relative effectiveness of substrate mixtures.