Freeze-Thaw Cycle-Enhanced Transformation of Iodide to Organoiodine Compounds in the Presence of Natural Organic Matter and Fe(III).

The formation of organoiodine compounds (OICs) is of great interest in the natural iodine cycle as well as water treatment processes. Herein, we report a pathway of OIC formation that reactive iodine (RI) and OICs are produced from iodide oxidation in the presence of Fe(III) and natural organic matter (NOM) in frozen solution, whereas their production is insignificant in aqueous solution. Moreover, thawing the frozen solution induces the further production of OICs. A total of 352 OICs are detected by Fourier transform ion cyclotron resonance mass spectrometry in the freeze-thaw cycled reactions of Fe(III)/I-/humic acid solution, which are five times as many as OICs in aqueous reactions. Using model organic compounds instead of NOM, aromatic compounds (e.g., phenol, aniline, o-cresol, and guaiacol) induce higher OIC formation yields (10.4-18.6%) in the freeze-thaw Fe(III)/I- system than those in aqueous (1.1-2.1%) or frozen (2.7-7.6%) solutions. In the frozen solution, the formation of RI is enhanced, but its further reaction with NOM is hindered. Therefore, the freeze-thaw cycle in which RI is formed in the frozen media and the resulting RI is consumed by reaction with NOM in the subsequently thawed solution is more efficient in producing OICs than the continuous reaction in frozen solution.

Cr(VI) Formation via Oxyhalide-Induced Oxidative Dissolution of Chromium Oxide/Hydroxide in Aqueous and Frozen Solution.

The oxidative dissolution of Cr(III) species (Cr2O3 and Cr(OH)3) by oxyhalide species, which produces hexavalent chromium (Cr(VI)), was studied in aqueous and frozen solution. The oxyhalide-induced oxidation of Cr(III) in frozen solution showed a different trend from that in aqueous solution. Cr(VI) production was higher in frozen than aqueous solution with hypochlorous acid (HOCl) and bromate (BrO3-) but suppressed in frozen solution with hypobromous acid (HOBr) and periodate (IO4-). In particular, bromate markedly enhanced Cr(VI) production in frozen solution, whereas it had a negligible activity in aqueous solution. On the contrary, periodate produced Cr(VI) significantly in aqueous solution but greatly suppressed it in frozen solution. Bromate was found to be much more concentrated in the ice grain boundary than periodate according to both chemical and Raman spectral analyses. The oxidative transformation of Cr(III) to Cr(VI) was accompanied by the concurrent and stoichiometric reduction of oxyhalide species. Dissolved O2 had little effect on the oxidative dissolution, but dissolved organic matter retarded the oxidation of Cr2O3 in both aqueous and frozen conditions. This study proposes that the oxyhalide-induced oxidation of Cr(III) (particularly by bromate) in frozen conditions might have a significant effect on the generation of Cr(VI) in the frozen environment.

Entangled iodine and hydrogen peroxide formation in ice.

Ice-core records show that anthropogenic pollution has increased the global atmospheric concentrations of hydrogen peroxide and iodine since the mid-20th century. Here, for the first time, we demonstrate a highly efficient mechanism that synergistically produces them in icy water conditions. This reaction is aided by a key intermediate IO2H, formed by an I- ion with a dissolved O2 in acidic icy water, which produces both I as well as O2H radicals. I recombines with I- to produce I2- at a diffusion-limited rate, followed by formation of I3- through disproportionation, while O2H yields H2O2 with I- and a proton dissolved in icy water.

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.

The effects of particle-induced oxidative damage from exposure to airborne fine particulate matter components in the vicinity of landfill sites on Hong Kong.

The physical, chemical and bioreactivity characteristics of fine particulate matter (PM2.5) collected near (<1 km) two landfill sites and downwind urban sites were investigated. The PM2.5 concentrations were significantly higher in winter than summer. Diurnal variations of PM2.5 were recorded at both landfill sites. Soot aggregate particles were identified near the landfill sites, which indicated that combustion pollution due to landfill activities was a significant source. High correlation coefficients (r) implied several inorganic elements and water-soluble inorganic ions (vanadium (V), copper (Cu), chloride (Cl-), nitrate (NO3-), sodium (Na) and potassium (K)) were positively associated with wind flow from the landfill sites. Nevertheless, no significant correlations were also identified between these components against DNA damage. Significant associations were observed between DNA damage and some heavy metals such as cadmium (Cd) and lead (Pb), and total Polycyclic Aromatic Hydrocarbons (PAHs) during the summer. The insignificant associations of DNA damage under increased wind frequency from landfills suggested that the PM2.5 loading from sources such as regional sources was possibly an important contributing factor for DNA damage. This outcome warrants the further development of effective and source-specific landfill management regulations for particulate matter production control to the city.

Abiotic Formation of Humic-Like Substances through Freezing-Accelerated Reaction of Phenolic Compounds and Nitrite.

A previously unknown abiotic humification pathway which is highly accelerated in frozen solution containing phenolic compounds and nitrite was investigated and proposed. The production of humic-like acids (HLA) and fulvic-like acids (FLA) was observed in the frozen solution (-20 °C) whereas it was negligible in aqueous solution (20 °C). Inorganic nitrogen was transformed into organic nitrogen during the humification process. Mass spectrometry (MS) and elemental analyses, including pyrolysis-GC/MS and FT-ion cyclotron resonance/MS, showed that humification products (HLA and FLA) have chemical structures and compositions similar to nature humic substances. The enhanced humification reaction could be attributed to the freeze-concentration effect, whereby nitrite ions in the unfrozen grain boundary region are transformed into nitrosonium ions which oxidize phenols to phenolic radicals. Confocal Raman microscopy confirmed that catechol and nitrite ions are preferentially concentrated at the ice grain boundary and electron paramagnetic resonance spectroscopic analysis of catechol/nitrite solution detected the phenolic radicals only in frozen solution, not in aqueous solution. The freezing-induced generation of phenolic radicals should lead to the formation of humic-like substances through polymerization. This study identifies and proposes a new humic formation pathway that might work as a model abiotic "bottom-up" mechanism in frozen environmental conditions.

Accelerated Reduction of Bromate in Frozen Solution.

Bromate is a common disinfection byproduct formed during ozonation. Reducing bromate into bromide can remove this toxic pollutant, however, not many studies have been done for its environmental fate. In this work, we demonstrate a new transformation pathway that bromate can be efficiently reduced to bromide in frozen solution in the presence of organic reductants like humic substances (HS). The results showed that bromate in frozen solution could be removed by 30-40% in dark condition and 80-90% in irradiation condition (λ > 300 nm) in 24 h, while around 1% bromate was reduced in aqueous solution. The bromate reduction by HS induced a partial oxidation of HS, which was confirmed by X-ray photoelectron spectroscopic analysis of the HS sample recovered from the frozen solution. Photoluminescence analysis of HS revealed that the fluorescence quenching by bromate was observed only with very high concentration of bromate (0.1-0.2 M) in aqueous solution whereas the quenching effect in frozen solution was seen with much lower bromate concentration (5-100 µM). The highly enhanced removal of bromate in ice is ascribed to the freeze concentration effect that bromate and HS are concentrated by orders of magnitude to accelerate the bimolecular transformation in the ice grain boundary region. Freezing process in cold environments would provide a unique chemical mechanism for the removal of persistent bromate.

Production of Molecular Iodine and Tri-iodide in the Frozen Solution of Iodide: Implication for Polar Atmosphere.

The chemistry of reactive halogens in the polar atmosphere plays important roles in ozone and mercury depletion events, oxidizing capacity, and dimethylsulfide oxidation to form cloud-condensation nuclei. Among halogen species, the sources and emission mechanisms of inorganic iodine compounds in the polar boundary layer remain unknown. Here, we demonstrate that the production of tri-iodide (I3(-)) via iodide oxidation, which is negligible in aqueous solution, is significantly accelerated in frozen solution, both in the presence and the absence of solar irradiation. Field experiments carried out in the Antarctic region (King George Island, 62°13'S, 58°47'W) also showed that the generation of tri-iodide via solar photo-oxidation was enhanced when iodide was added to various ice media. The emission of gaseous I2 from the irradiated frozen solution of iodide to the gas phase was detected by using cavity ring-down spectroscopy, which was observed both in the frozen state at 253 K and after thawing the ice at 298 K. The accelerated (photo-)oxidation of iodide and the subsequent formation of tri-iodide and I2 in ice appear to be related with the freeze concentration of iodide and dissolved O2 trapped in the ice crystal grain boundaries. We propose that an accelerated abiotic transformation of iodide to gaseous I2 in ice media provides a previously unrecognized formation pathway of active iodine species in the polar atmosphere.

Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions.

Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.