Yuqiu Wan

Adsorption of Tetracycline and Sulfamethoxazole on Crop Residue-Derived Ashes: Implication for the Relative Importance of Black Carbon to Soil Sorption

The main objective of this study was to investigate the key factors and mechanisms of antibiotic adsorption on crop residue-derived black carbon, as well as the relative importance of black carbon to the overall sorption to soil. Batch sorption experiments were performed for two reference antibiotics (sulfamethoxazole and tetracycline) on wheat- and maize-residue-derived black carbon. After removal of the mineral fraction from the raw black carbon by acidification, tetracycline exhibited less enhanced adsorption than sulfamethoxazole, implying stronger complexation of tetracycline on the mineral components. The antibiotic adsorption on the demineralized black carbon was very strong (The measured K(d) was in the order of 10(3)-10(5) L/kg). The adsorbent surface area-normalized adsorption of sulfamethoxazole was higher on the demineralized black carbon than on nonporous graphite due to the micropore-filling effect. The opposite trend observed for bulky tetracycline was attributed to the size-exclusion effect. Owing to the strong surface complexation and/or cation exchange reaction, sorption of tetracycline to Na(+)-exchanged montmorillonite, soil humic acids, and bulk soil was remarkably stronger than sulfamethoxazole. It was estimated that the contribution of black carbon to the overall sorption to bulk soil was important for sulfamethoxazole, but negligible for tetracycline.

Adsorption of pharmaceuticals to microporous activated carbon treated with potassium hydroxide, carbon dioxide, and steam.

Adsorption of sulfapyridine, tetracycline, and tylosin to a commercial microporous activated carbon (AC) and its potassium hydroxide (KOH)-, CO-, and steam-treated counterparts (prepared by heating at 850°C) was studied to explore efficient adsorbents for the removal of selected pharmaceuticals from water. Phenol and nitrobenzene were included as additional adsorbates, and nonporous graphite was included as a model adsorbent. The activation treatments markedly increased the specific surface area and enlarged the pore sizes of the mesopores of AC (with the strongest effects shown on the KOH-treated AC). Adsorption of large-size tetracycline and tylosin was greatly enhanced, especially for the KOH-treated AC (more than one order of magnitude), probably due to the alleviated size-exclusion effect. However, the treatments had little effect on adsorption of low-size phenol and nitrobenzene due to the predominance of micropore-filling effect in adsorption and the nearly unaffected content of small micropores causative to such effect. These hypothesized mechanisms on pore-size dependent adsorption were further tested by comparing surface area-normalized adsorption data and adsorbent pore size distributions with and without the presence of adsorbed antibiotics. The findings indicate that efficient adsorption of bulky pharmaceuticals to AC can be achieved by enlarging the adsorbent pore size through suitable activation treatments.

Enhanced adsorption of humic acids on ordered mesoporous carbon compared with microporous activated carbon

Humic acids are ubiquitous in surface and underground waters and may pose potential risk to human health when present in drinking water sources. In this study, ordered mesoporous carbon was synthesized by means of a hard template method and further characterized by X-ray diffraction, N2 adsorption, transition electron microscopy, elemental analysis, and zeta-potential measurement. Batch experiments were conducted to evaluate adsorption of two humic acids from coal and soil, respectively, on the synthesized carbon. For comparison, a commercial microporous activated carbon and nonporous graphite were included as additional adsorbents; moreover, phenol was adopted as a small probe adsorbate. Pore size distribution characterization showed that the synthesized carbon had ordered mesoporous structure, whereas the activated carbon was composed mainly of micropores with a much broader pore size distribution. Accordingly, adsorption of the two humic acids was substantially lower on the activated carbon than on the synthesized carbon, because of the size-exclusion effect. In contrast, the synthesized carbon and activated carbon showed comparable adsorption for phenol when the size-exclusion effect was not in operation. Additionally, we verified by size-exclusion chromatography studies that the synthesized carbon exhibited greater adsorption for the large humic acid fraction than the activated carbon. The pH dependence of adsorption on the three carbonaceous adsorbents was also compared between the two test humic acids. The findings highlight the potential of using ordered mesoporous carbon as a superior adsorbent for the removal of humic acids.

Enhanced photocatalytic reduction of aqueous Pb(II) over Ag loaded TiO2 with formic acid as hole scavenger

In the present study, photocatalytic Pb(II) reduction over TiO2 and Ag/TiO2 catalysts in the presence of formic acid was explored to eliminate Pb(II) pollution in water. Ag/TiO2 catalysts were prepared by the photo-deposition method and characterized using UV-Vis diffuse reflectance spectra, X-ray reflection diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Ag deposition on TiO2 led to enhanced photocatalytic Pb(II) reduction and the Ag/TiO2 catalyst with a Ag loading amount of 0.99 wt.% exhibited the optimum photocatalytic activity. For Pb(II) reduction over Ag/TiO2 with a Ag loading amount of 0.99 wt.%, initial Pb(II) reduction rate was found to be dependent on the initial concentrations of formic acid and Pb(II). Increasing initial Pb(II) concentration led to linearly increased initial Pb(II) reduction rate. At low formic acid concentration, in parallel, initial Pb(II) reduction rates increased with formic concentration, but remained nearly identical at high formic acid concentration. Solution pH impacted the photocatalytic Pb(II) reduction and after irradiation for 100 min Pb(II) was removed by 11.8%, 91.2% and 98.6% at pH of 0.8, 2.0 and 3.5, respectively, indicative of enhanced Pb(II) reduction with pH in the tested pH range. The results showed that Ag/TiO2 displayed superior catalytic activity to TiO2, highlighting the potential of using Ag/TiO2 as a more effective catalyst for photocatalytic Pb(II) reduction.

Sorption of aromatic ionizable organic compounds to montmorillonites modified by hexadecyltrimethyl ammonium and polydiallyldimethyl ammonium.

Environmental residues of aromatic ionizable organic compounds (AIOCs) have received considerable attention due to their potential human health and ecological risks. The main objective of this study was to investigate the key factors and mechanisms controlling sorption of a series of anionic and zwitterionic AIOCs (two aromatic sulfonates, 4-methyl-2,6-dinitrophenol, tetracycline, sulfamethoxazole, and tannic acid) to montmorillonites modified with hexadecyltrimethyl ammonium (HDTMA) and polydiallyldimethyl ammonium (PDADMA). Compared with naphthalene (a nonpolar and nonionic solute), all AIOCs showed stronger sorption (the sorbent-to-solution distribution coefficient was in the order of 10-10 L kg) to the two organoclays in spite of the much lower hydrophobicity, indicating the predominance of electrostatic interaction in sorption. The proposed electrostatic mechanism of the tested AIOCs was supported by the pH dependency of sorption to the two organoclays. The two organoclays manifested weaker sorption affinity but faster sorption kinetics for bulky AIOCs than commercial activated carbon, resulting from the high accessibility of sorption sites in the open, ordered clay interlayer. The findings of this study highlight the potential of using HDTMA- and PDADMA-exchanged montmorillonites as effective sorbents for AIOCs in water and wastewater treatments.

Effect of Heat Treatment on Sorption of Polar and Nonpolar Compounds to Montmorillonites and Soils

Batch sorption isotherms of 1,3,5-trichlorobenzene, 1,3,5-trinitrobenzene, and tetracycline to organic-free montmorillonites and soils receiving heat treatment (375°C for 24 h) were compared with those to unheated sorbents. Sorption of the nonpolar 1,3,5-trichlorobenzene to soil was lowered after the removal of humus by heating, consistent with the mechanism of hydrophobic partition into organic matter. For 1,3,5-trinitrobenzene, the enhanced sorption to heated soils was attributed to specific interactions with exchangeable cations facilitated by heating-induced irreversible partial dehydration of the clay interlayer. For tetracycline, an additional mechanism for sorption enhancement could be due to increased exposure of strong complexation sites on clay minerals after removal of the humic coating. These hypotheses were supported by the sorption data to heated and unheated Na-, K-, and Cs-saturated montmorillonites. The combustion method is commonly adopted to measure the content of black carbon in soils and sediments. However, findings from the present study indicate that combustion may greatly modify the structural properties of clay minerals, leading to misinterpreted sorption contributions of different soil components to sorption of polar or ionic compounds.

ZrO2 nanoparticles confined in metal organic frameworks for highly effective adsorption of phosphate

Highly dispersed ZrO2 particles confined in the MIL-101 (denoted as MIL-101@Zr(DS)) with varied ZrO2 loading amounts were prepared by the double solvents method. For comparison, ZrO2 loaded MIL-101 samples were synthesized by the conventional impregnation method (denoted as MIL-101@Zr(I)) and the deposition method (denoted as MIL-101@Zr(D)). The characterization results indicated that for MIL-101@Zr(DS), ZrO2 particles were dominantly confined in MIL-101 with a much higher dispersion as compared with MIL-101@Zr(I) and MIL-101@Zr(D). The maximum phosphate adsorption capacity and ZrO2 content normalized phosphate adsorption capacity of the MIL-101@Zr(DS) were 21.28 mg P·g-1 and 1120.0 mg P·g-1, respectively. Additionally, the ZrO2 content normalized phosphate adsorption capacity was significantly larger than that for MIL-101@Zr(I) and MIL-101@Zr(D) as well as the reported values for other Zr-based adsorbents. The effects of solution chemistry on phosphate adsorption to MIL-101@Zr(DS), MIL-101@Zr(I) and MIL-101@Zr(D) were also examined. Compared with MIL-101@Zr(I) and MIL-101@Zr(D), the adsorption of phosphate on MIL-101@Zr(DS) was less affected by the coexistence of anions and dissolved humic acid. Increasing pH from 3 to 12 led to decreased phosphate adsorption capacity of MIL-101@Zr(DS) from 10.38 mg P·g-1 to 2.03 mg P·g-1. Accordingly, used MIL-101@Zr(DS) could be effectively regenerated under alkaline conditions and exhibited stable adsorption-desorption performance.