Simultaneous and Synergic Production of Bioavailable Iron and Reactive Iodine Species in Ice.

The bioavailable iron is essential for all living organisms, and the dissolution of iron oxide contained in dust and soil is one of the major sources of bioavailable iron in nature. Iodine in the polar atmosphere is related to ozone depletion, mercury oxidation, and cloud condensation nuclei formation. Here we show that the chemical reaction between iron oxides and iodide (I-) is markedly accelerated to produce bioavailable iron (Fe(II)aq) and tri-iodide (I3-: evaporable in the form of I2) in frozen solution (both with and without light irradiation), while it is negligible in aqueous phase. The freeze-enhanced production of Fe(II)aq and tri-iodide is ascribed to the freeze concentration of iron oxides, iodides, and protons in the ice grain boundaries. The outdoor experiments carried out in midlatitude during a winter day (Pohang, Korea: 36°0' N, 129°19' E) and in an Antarctic environment (King George Island: 62°13' S 58°47' W) also showed the enhanced generation of Fe(II)aq and tri-iodide in ice. This study proposes a previously unknown abiotic mechanism and source of bioavailable iron and active iodine species in the polar environment. The pulse input of bioavailable iron and reactive iodine when ice melts may influence the oceanic primary production and CCN formation.

Ligand-Specific Dissolution of Iron Oxides in Frozen Solutions.

The freezing-enhanced dissolution of iron oxides by various ligands has been recently proposed as a new mechanism that may influence the supply of bioavailable iron in frozen environments. The ligand-induced dissolution of iron oxides is sensitively affected by the kind and concentration of ligands, pH, and kind of iron oxides. While most ligands are thought to be freeze-concentrated in the ice grain boundary region along with iron oxides to enhance the iron dissolution, this study found that some ligands, such as ascorbic acid, suppress the iron dissolution in frozen solution relative to that in aqueous solution. Such ligands are proposed to be preferentially incorporated in the ice lattice bulk and not freeze-concentrated in the liquid-like grain boundary. The experimental analysis estimated that the ionized forms of ligands (e.g., iodide ions) are hardly present in the ice bulk region (<3%) and enhance the iron dissolution in frozen solution (relative to that in aqueous solution), whereas some neutral ligands (e.g., undissociated ascorbic acid) are significantly trapped in the ice bulk (>50%) and suppress the iron dissolution compared to the aqueous counterpart. The present results reveal that the ligand-induced dissolution of iron oxide in frozen solution is not always enhanced relative to aqueous solution but depends upon the kind of ligand and experimental conditions.

Selective accumulation of pharmaceutical residues from 6 different soils by plants: a comparative study on onion, radish, and spinach.

The accumulation of six pharmaceuticals of different therapeutic uses has been thoroughly investigated and compared between onion, spinach, and radish plants grown in six soil types. While neutral molecules (e.g., carbamazepine (CAR) and some of its metabolites) were efficiently accumulated and easily translocated to the plant leaves (onion > radish > spinach), the same for ionic (both anionic and cationic) molecules seems to be minor to moderate. The maximum accumulation of CAR crosses 38,000 (onion), 42,000 (radish), and 7000 (spinach) ng g-1 (dry weight) respectively, in which the most majority of them happened within the plant leaves. Among the metabolites, the accumulation of carbamazepine 10,11-epoxide (EPC - a primary CAR metabolite) was approximately 19,000 (onion), 7000 (radish), and 6000 (spinach) ng g-1 (dry weight) respectively. This trend was considerably similar even when all these pharmaceuticals applied together. The accumulation of most other molecules (e.g., citalopram, clindamycin, clindamycin sulfoxide, fexofenadine, irbesartan, and sulfamethoxazole) was restricted to plant roots, except for certain cases (e.g., clindamycin and clindamycin sulfoxide in onion leaves). Our results clearly demonstrated the potential role of this accumulation process on the entrance of pharmaceuticals/metabolites into the food chain, which eventually becomes a threat to associated living biota.

Dissipation of twelve organic micropollutants in three different soils: Effect of soil characteristics and microbial composition.

The dissipation kinetics and half-lives of selected organic micropollutants, including pharmaceuticals and others, were systematically investigated and compared among different soil types. While some pollutants (e.g., atorvastatin, valsartan, and bisphenol S) disappeared rapidly in all the tested soils, many of them (e.g., telmisartan, memantine, venlafaxine, and azithromycin) remained persistent. Irrespective of the soil characteristics, venlafaxine showed the lowest dissipation kinetics and the longest half-lives (250 to approximately 500 days) among the stable compounds. The highest first and second-order kinetics were, however, recorded for valsartan (k1; 0.262 day-1) and atorvastatin (k2; 33.8 g µg-1 day-1) respectively. Nevertheless, more than 90% (i.e., DT90) of all the rapidly dissipated compounds (i.e., atorvastatin, bisphenol S, and valsartan) disappeared from the tested soils within a short timescale (i.e., 5-36 days). Dissipation of pollutants that are more susceptible to microbial degradation (e.g., atorvastatin, bisphenol S, and valsartan) seems to be slower for soils possessing the lowest microbial biomass C (Cmic) and total phospholipid fatty acids (PLFAtotal), which also found statistically significant. Our results revealing the persistence of several organic pollutants in agricultural soils, which might impact the quality of these soils, the groundwater, and eventually on the related biota, is of high environmental significance.

Sonochemical degradation of benzenesulfonic acid in aqueous medium.

Degradation of benzenesulfonic acid (BSA), the simplest aromatic sulfonic acid with extreme industrial importantance, by sonochemically generated hydroxyl radical (OH) have been thoroughly investigated. A reasonable reduction (∼50%) in the total organic carbon (TOC) was achieved only after prolonged irradiation (∼275 min, 350 kHz) of ultrasound, although a short irradiation of less than an hour is enough to degrade significant amount of BSA. The degradation efficiency of ultrasound has been reduced in lower and extremely higher frequencies, and upon increasing the pH. An irregular, but continuous, release of sulfate ions was also observed. Further, the release of protons upon the oxidation of BSA consistently reduces the experimental pH to nearly 2. High resolution mass spectrometric (HRMS) analyses reveals the formation of a number of aromatic intermediates, including three mono (Ia-c) and two di (IIa&b) hydroxylated BSA derivatives as the key products in the initial stages of the reaction. Pulse radiolysis studies revealed the generation of hydroxycyclohexadienyl-type radicals, characterized by absorption bands at 320 nm (k2 = (7.16 ± 0.04) × 109 M-1 s-1) and 380 nm, as the immediate intermediates of the reaction. The mechanism(s) leading to the degradation of BSA under sonolytic irradiation conditions along with the effect of various factors, such as the ultrasound frequency and reaction pH, have been explained in detail. The valuable mechanistic aspects obtained from our pulse radiolysis and HRMS studies are essential for the proper implementation of sonochemical techniques into real water purification process and, thus, receives extreme environmental relevance.

Halide-induced dissolution of lead(IV) oxide in frozen solution.

The dark dissolution behavior of plattnerite (ß-PbO2) was investigated in frozen solutions containing halide ions and compared with those in aqueous solution. The amount of dissolved lead in the frozen solutions varied depending on the solution pH and the kind and concentration of halide ions. The presence of bromide and iodide ions enhanced the dissolution of lead in the aqueous phase, whereas the effect of chloride was insignificant. Compared with the aqueous phase dissolution, ß-PbO2 dissolution in the frozen solution was slightly enhanced in the presence of bromide but suppressed in the presence of iodide. Iodide ions seemed to be relatively more trapped in the bulk ice (ice-crystal lattice) than bromide ions, which might be related to the suppressed dissolution of lead oxide in the presence of iodide. The co-existence of bromide (or iodide) and chloride ions in the frozen solution enhanced the dissolution of lead, which seems to be enabled by an additional reaction pathway involving the formation of mixed halide radicals, whereas such kind of synergistic enhancements were not observed in aqueous solution. The halide-induced lead oxide dissolution in frozen solutions can be related to the behavior of lead ions found in various media of frozen environments.