Evidence of singlet oxygen and hydroxyl radical formation in aqueous goethite suspension using spin-trapping electron paramagnetic resonance (EPR)

The generation of reactive species in an aqueous goethite suspension, under room light and aeration conditions, was investigated using the electron paramagnetic resonance (EPR) technique employing spin trap agents. The trap reagents, including 5,5-dimethylpyrroline N-oxide (DMPO) and 2,2,6,6-tetramethylpiperidine (TEMP), were used for the detection of OH radicals (OH) and singlet oxygen (¹O₂), respectively. On the addition of DMPO to the goethite suspended solution, a DMPO-OH adduct was formed, which was not decreased, even in the presence of the OH scavenger, mannitol. This result implied a false positive interpretation from the DMPO-OH EPR signal. In the presence of TEMP reagent, a TEMP-O signal was detected, which was completely inhibited in the presence of the singlet oxygen scavenger, sodium azide. With both DMPO-OH and TEMP-O radicals in the presence and absence of radical scavengers, singlet oxygen was observed to be the key species formed in the room-light sensitized goethite suspension. In the goethite/H₂O₂ system; however, both OH and singlet oxygen were generated, with significant portions of DMPO-OH resulting from both OH and singlet oxygen. In fact, the DMPO-OH resulting from OH should be carefully calculated by correcting for the amount of DMPO-OH due to singlet oxygen. This study reports, for the first time, that the goethite suspensions may also act as a natural sensitizer, such as fulvic acids, to form singlet oxygen.     

The impact of heavy metal pollution gradients in sediments on benthic macrofauna at population and community levels

The effect of sediment pollution on benthos was investigated in the vicinity of a large sewage treatment outflow at Incheon North Harbor, Korea. Animal size, vertical distribution and standard community parameters were analyzed along a 3 km transect line (n = 7). Univariate parameters showed a general trend of increasing species diversity with increasing distance from the pollution source. Multi-dimensional scaling analysis led to the clear separation of 3 locational groups, supporting gradient-dependent faunal composition. The innermost location was dominated by small sub-surface dwellers while the outer locations by large mid to deep burrowers. Looking for the size-frequency distribution, most abundance species (Heteromastus filiformis) showed the presence of larger size animals with increasing proximity to the pollution source. Meanwhile, species-specific vertical distributions, regardless of the pollution gradient, indicated that such shifts were due to species replacement resulting from a higher tolerance to pollutants over some species.     

Human exposure to PCDDs, PCDFs and dioxin-like PCBs associated with seafood consumption in Korea from 2005 to 2007

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DLPCBs) were measured in 26 seafoods commonly consumed by the Korean population. The total toxic equivalent (TEQ) concentrations in seafood samples ranged from 0.01 to 6.76 pg TEQ/g wet wt, which were comparable with those found in other countries. The predominant congeners found in seafood samples were 2, 3, 4, 7, 8-PeCDF and 2, 3, 7, 8-TCDF for PCDD/Fs and PCB 118 for DLPCBs. Dietary intakes of PCDD/Fs and DLPCBs from seafood consumption were estimated for various age groups and gender in Korea. The dietary intake of PCDD/Fs and DLPCBs from seafood consumption for the general population was estimated to be 1.23 pg TEQ/kg bw/day, values that are in the range of those reported for other countries. Mackerel, tuna and hairtail contributed to the highest TEQ intakes, which collectively accounted for 66% of the total intake. Among the eight age groups investigated, 3-6 year old children had the highest TEQ exposure, followed by 50-64 years, 30-39 years and <2 years. Considering contributions of seafood consumption to the total dietary intake studies, the dietary TEQ intakes to the general population appear to be below the threshold values by international organizations. The present study may be useful for risk management for dioxins and dioxin-like contaminants in Korean seafood.     

Application of TRIZ creativity intensification approach to chemical process safety

This study develops a modified method of TRIZ to improve safety in chemical process design. This method is modified by the theory of TRIZ, which is inventive problem solving theory, for retrofit design of chemical process considering safety.The original TRIZ is difficult to access to chemical process safety due to inapplicability and ambiguity of terminology in classification of these parameters. It is necessary to be modified TRIZ for chemical process safety. This study reorganized thirty-nine parameters of the TRIZ into six categories such as mechanic, operator, process upset, design, natural hazard and material. The modified TRIZ is tested to jacketed reactor and polyethylene reactor.     

Indoor radon distribution of subway stations in a Korean major city

The overall survey on indoor radon concentration was conducted at all subway stations in a major city, Daejeon in the central part of Korea. It was quarterly performed from September 2007 to August 2008. The annual arithmetic mean of indoor radon concentration of all the stations was 34.1 ± 14.7 Bq m⁻³, and the range of values was from 9.4 to 98.2 Bq m⁻³. The radon concentrations in groundwater (average 31.0 ± 0.8 Bq m⁻³) were not significantly high in most stations, but the concentration (177.9 ± 2.3 Bq L⁻¹) of one station was over the level of 148 Bq L⁻¹ in drinking water proposed by U.S. EPA. Based on indoor survey results, the approximate average of the annual effective dose by radon inhalation to the employees and passengers were 0.24 mSv y⁻¹, and 0.02 mSv y⁻¹, respectively. Although the effective dose based on the UNSCEAR report was potentially estimated, for more accurate assessment, the additional survey on the influence by indoor radon will be necessary.     

Cesium and strontium sorption by selected tropical and subtropical soils around nuclear facilities

The dynamics of Cs and Sr sorption by soils, especially in the subtropics and tropics, as influenced by soil components are not fully understood. The rates and capacities of Cs and Sr sorption by selected subtropical and tropical soils in Taiwan were investigated to facilitate our understanding of the transformation and dynamics of Cs and Sr in soils developed under highly weathering intensity. The Langmuir isotherms and kinetic rates of Cs and Sr sorption on the Ap1 and Bt1 horizons of the Long-Tan (Lt) and the A and Bt1 horizons of the Kuan-Shan (Kt), Mao-Lin (Tml) and Chi-Lo (Cl) soils were selected for this study. Air-dried soil (<2 mm) samples were reacted with of 7.5 × 10⁻⁵ to 1.88 × 10⁻³ M of CsCl (pH 4.0) or 1.14 × 10⁻⁴ to 2.85 × 10⁻³ M of SrCl₂ (pH 4.0) solutions at 25 °C. The sorption maximum capacity (q_m) of Cs by the Ap1 and Bt1 horizons of the Lt soil (62.24 and 70.70 mmol Cs kg⁻¹ soil) were significantly (p < 0.05) higher than those by the A and Bt1 horizons of the Kt and Cl soils (26.46 and 27.49 mmol Cs kg⁻¹ soil in Kt soil and 34.83 and 29.96 mmol Cs kg⁻¹ soil in Cl soil, respectively), however, the sorption maximum capacity values of the Lt and Tml soils did not show significant differences. The amounts of pyrophosphate extractable Fe (Fe_p) were correlated significantly with the Cs and Sr sorption capacities (for Cs sorption, r² = 0.97, p < 1.0 × 10⁻⁴; for Sr sorption, r² = 0.82, p < 2.0 × 10⁻³). The partition coefficient of radiocesium sorbed on soil showed the following order: Cl soil ? Kt soil > Tml soil > Lt soil. It was due to clay minerals. The second-order kinetic model was applied to the Cs and Sr sorption data. The rate constant of Cs or Sr sorption on the four soils was substantiality increased with increasing temperature. This is attributable to the availability of more energy for bond breaking and bond formation brought about by the higher temperatures. The rate constant of Cs sorption at 308 K was 1.39-2.09 times higher than that at 278 K in the four soils. The activation energy of Cs and Sr sorbed by the four soils ranged from 7.2 to 16.7 kJ mol⁻¹ and from 15.2 to 22.4 kJ mol⁻¹, respectively. Therefore, the limiting step of the Cs⁺ or Sr²⁺ sorption on the soils was diffusion-controlled processes. The reactive components, which are significantly correlated with the Langmuir sorption maxima of Cs and Sr by these soils, substantially influenced their kinetic rates of Cs and Sr sorption. The data indicate that among components of the subtropical and tropical soils studied, short-range ordered sesquioxides especially Al- and Fe-oxides complexed with organics play important roles in influencing their capacity and dynamics of Cs and Sr sorption.     

1H-NMR-based metabolomic study on toxicity of methomyl and methidathion in fish

A ¹H-nuclear magnetic resonance (NMR) spectroscopy with multivariate analysis was applied to detect the toxicity of antiacetylcholinesterase insecticides, methomyl (methyl (1E)-N-(methylcarbamoyloxy)ethanimidothioate) and methidathion (3-(dimethoxyphosphinothioyl sulfanylmethyl)-5-methoxy-1,3,4-thiadiazol-2-one), using zebrafish (Danio rerio) and Chinese bleak (Aphyocypris chinensis). Generally, methomyl and methidathion have been believed not to highly accumulate in fish tissues. However, these pesticides showed their toxicity by altering patterns of whole-body metabolites in neurotransmitter balance, energy metabolism, oxidative stress, and muscle maintenance in low concentrations. We used Pearson correlation analysis to contextualize the metabolic markers in pesticide treated groups. We observed that the positive correlations of choline with acetate and betaine in untreated control were shifted to null correlations showing acetylcholinesterase specific toxicity. This research demonstrated the applicability and potential of NMR metabolomics in detecting toxic effects of insecticide with a modicum of concentrations in aquatic environment.     

Effect of incineration on the removal of key offensive odorants released from a landfill leachate treatment station (LLTS)

As a basic means to control odorants released from a landfill leachate treatment station (LLTS), effluents venting from this station were treated via incineration with methane rich landfill gas (at 750 °C). A list of the key offensive odorants covering 22 chemicals was measured by collecting those gas samples both before and after the treatment. Upon incineration, the concentration levels of most odorants decreased drastically below threshold levels. The sum of odorant intensities (SOIs), if compared between before and after incineration, decreased from 6.94 (intolerable level) to 3.45 (distinct level). The results indicate that the thermal incineration method can be used as a highly efficient tool to remove most common odorants (e.g., reduced sulfur species), while it is not so for certain volatile species (e.g., carbonyls, fatty acids, etc.).     

Enzymatic and microbial transformation assays for the evaluation of the environmental fate of diclofenac and its metabolites

Diclofenac has been of environmental concern due to the potential harmful effects on non-target organisms at environmentally relevant concentrations. In this study, we evaluated the transformation kinetics of diclofenac and its two major metabolites in two laboratory-scale experiments: the transformation of diclofenac in the presence of rat liver S9 fraction with co-factors, and the transformation of diclofenac, 4′-hydroxy-diclofenac and diclofenac β-O-acyl glucuronide in the inoculum used for the OECD 301C ready-biodegradability test. 4′-Hydroxy-diclofenac was identified as the major phase I metabolite and diclofenac β-O-acyl glucuronide was identified as the major phase II metabolite in the S9 assay. Transformation of diclofenac in the microbial degradation test did not occur significantly for 28 d, whereas 4′-hydroxy-diclofenac degraded slowly, indicating that the biological removal of diclofenac is not likely to occur in conventional STPs unless sorptive removal is significant. However, diclofenac β-O-acyl glucuronide deconjugated to form equimolar diclofenac within 7 d, in the microbial degradation test. The mixture of diclofenac and its two metabolites, formed after incubating diclofenac in S9 medium for 2 h, was spiked in the inoculum to link both assays. The concentrations of diclofenac and its metabolites, measured over time, agreed well with predicted values, using rate parameters obtained from independent experiments. The results show that phase II metabolites generated in mammals may deconjugate easily in conventional STPs to form a parent compound and that these processes should be considered during the environmental monitoring and risk assessment of diclofenac.