Optimization of Iron Removal in the Recovery of Rare-Earth Elements from Coal Fly Ash Using a Recyclable Ionic Liquid.

Rare-earth elements (REEs) are essential for modern technologies, and the United States currently lacks a secure domestic supply. Coal combustion residuals, specifically coal fly ash (CFA), can be a potential source. Our previous work demonstrated that REEs could be preferentially extracted from CFA using the ionic liquid (IL) betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]), and the process yielded a mildly acidic REE-rich solution with coextracted Fe and regenerated IL. In this study, we investigated three strategies to limit Fe coextraction: magnetic separation, complexing salts, and ascorbic acid (AA) reduction. Magnetic separation of CFA was ineffective in significantly lowering the Fe content in the IL phase. When NaCl was used instead of NaNO3 during extraction, chloride complexation lowered iron distribution to the IL phase over the aqueous phase (DFe) by five folds, from ∼75 to ∼14, while REE leaching (LREEs) and recovery (RREEs) both increased. Using AA for iron reduction lowered the overall amount of Fe extracted and further decreased DFe to ∼0.16, effectively shifting Fe preference from the IL phase to the aqueous phase. Combining the strategies of NaCl, AA, and supplemental betaine addition, leaching and extraction of REEs from CFA by [Hbet][Tf2N] were achieved in higher efficiency for REE recovery with minimized Fe concentration.

UV/H2O2 and UV/PDS Treatment of Trimethoprim and Sulfamethoxazole in Synthetic Human Urine: Transformation Products and Toxicity.

Elimination of pharmaceuticals in source-separated human urine is a promising approach to minimize the pharmaceuticals in the environment. Although the degradation kinetics of pharmaceuticals by UV/H2O2 and UV/peroxydisulfate (PDS) processes has been investigated in synthetic fresh and hydrolyzed urine, comprehensive evaluation of the advanced oxidation processes (AOPs), such as product identification and toxicity testing, has not yet been performed. This study identified the transformation products of two commonly used antibiotics, trimethoprim (TMP) and sulfamethoxazole (SMX), by UV/H2O2 and UV/PDS in synthetic urine matrices. The effects of reactive species, including •OH, SO4(•-), CO3(•-), and reactive nitrogen species, on product generation were investigated. Multiple isomeric transformation products of TMP and SMX were observed, especially in the reaction with hydroxyl radical. SO4(•-) and CO3(•-) reacted with pharmaceuticals by electron transfer, thus producing similar major products. The main reactive species deduced on the basis of product generation are in good agreement with kinetic simulation of the advanced oxidation processes. A strain identified as a polyphosphate-accumulating organism was used to investigate the antimicrobial activity of the pharmaceuticals and their products. No antimicrobial property was detected for the transformation products of either TMP or SMX. Acute toxicity employing luminescent bacterium Vibrio qinghaiensis indicated 20-40% higher inhibitory effect of TMP and SMX after treatment. Ecotoxicity was estimated by quantitative structure-activity relationship analysis using ECOSAR.

Surface adsorption of organoarsenic roxarsone and arsanilic acid on iron and aluminum oxides.

Aromatic organoarsenicals roxarsone (ROX) and p-arsanilic acid (ASA) are common feed additives for livestock and could be released into the environment via animal manure and agricultural runoff. To evaluate their environmental fate, the adsorption behavior of ROX and ASA was investigated with two common soil metal oxides, goethite (FeOOH) and aluminum oxide (Al(2)O(3)), under different reactant loading, water pH and competing ion conditions. ROX and ASA exhibit essentially identical adsorption characteristics. FeOOH and Al(2)O(3) exhibit similar adsorption trends for both organoarsenicals; however, the adsorption efficiency on the surface site basis was about three times lower for Al(2)O(3) than for FeOOH. The adsorption reaction is favorable at neutral and acidic pH. Phosphate and natural organic matter significantly interfere with aromatic arsenical adsorption on both metal oxides, whereas sulfate and nitrate do not. Pre-adsorbed aromatic arsenicals can be quickly but not completely displaced by phosphate, indicating that ion exchange is not the only mechanism governing the adsorption process. The adsorption envelope was successfully modeled by a diffuse double layer surface complexation model, identifying the critical role of di-anionic organoarsenic species in the adsorption. Results of this research can help predict and control the mobility of aromatic arsenicals in the environment.

Adsorption and transformation of tetracycline antibiotics with aluminum oxide.

Tetracycline antibiotics (TCs) including tetracycline (TTC), chlorotetracycline (CTC) and oxytetracycline (OTC) adsorb strongly to aluminum oxide (Al(2)O(3)), and the surface interaction promotes structural transformation of TCs. The latter phenomenon was not widely recognized previously. Typically, rapid adsorption of TCs to Al(2)O(3) occurs in the first 3h ([TC]=40microM, [Al(2)O(3)]=1.78gL(-1), pH=5, and T=22 degrees C), followed by continuous first-order decay of the parent compound (k(obs)=15+/-1.0, 18+/-1.0 and 6.2+/-0.9x10(-3)h(-1) for TTC, CTC and OTC, respectively) and product formation. The transformation reaction rate of TCs strongly correlates with adsorption to Al(2)O(3) surfaces. Both adsorption and transformation occur at the highest rate at around neutral pH conditions. Product evaluation indicates that Al(2)O(3) promotes dehydration of TTC to yield anhydrotetracycline (AHTTC), epimerization of TTC, and formation of Al-TTC complexes. Al(2)O(3) promotes predominantly the transformation of CTC to iso-CTC. The surface-bound Al(+III) acts as a Lewis acid site to promote the above transformation of TCs. Formation of AHTTC is of special concern because of its higher cytotoxicity. Results of this study indicate that aluminum oxide will likely affect the fate of TC antibiotics in the aquatic environment via both adsorption and transformation.

The natural flavonoid apigenin suppresses Th1- and Th2-related chemokine production by human monocyte THP-1 cells through mitogen-activated protein kinase pathways.

Dietary flavonoids have various biological functions, and there is increasing evidence that reduced prevalence and severity of allergic reactions are associated with the intake of flavonoids. Among natural flavonoids, apigenin is a potent anti-inflammatory agent. However, the mechanisms of apigenin's effect remain uncertain. Monocyte-derived chemokine (MDC) plays a pivotal role in recruiting T-helper (Th) 2 cells in the allergic inflammation process. In the late phase of allergic inflammation, the Th1 chemokine interferon-inducible protein 10 (IP-10) has also been found in elevated levels in the bronchial alveolar fluid of asthmatic children. We used human THP-1 monocyte cells, pretreated with or without apigenin, prior to lipopolysaccharide stimulation. By means of enzyme-linked immunosorbent assay, we found that apigenin inhibited production of both MDC and IP-10 by THP-1 cells and that the suppressive effect of apigenin was not reversed by the estrogen receptor antagonist ICI182780. The p65 phosphorylation of nuclear factor kappaB remained unaffected, but the phosphorylation of p38, c-Jun N-terminal kinase, and extracellular signal-regulated kinase mitogen-activated protein kinase pathways were all blocked. We found that inhibition of c-raf phosphorylation might be the target of apigenin's anti-inflammation property.