Odd-numbered perfluorocarboxylates predominate over perfluorooctanoic acid in serum samples from Japan, Korea and Vietnam

Perfluorooctanoic acid (PFOA) has recently attracted attention as a potential health risk following environmental contamination. However, information detailing exposure to perfluorinated carboxylic acids (PFCAs) other than PFOA is limited. We measured the concentrations of PFCAs (from perfluorohexanoic acid to perfluorotetradecanoic acid) in serum samples obtained from patients in Japan (Sendai, Takayama, Kyoto and Osaka) between 2002 and 2009, Korea (Busan and Seoul) between 1994 and 2008 and Vietnam (Hanoi) in 2007/2008. Total PFCA levels (geometric mean) were increased from 8.9 ng mL(-1) to 10.3 ng mL(-1) in Japan; from 7.0 ng mL(-1) to 9.2 ng mL(-1) in Korea; and were estimated at 4.7 ng mL(-1) in Vietnam. PFCAs of greater length than PFOA were significantly increased in Sendai, Takayama and Kyoto, Japan, and levels of long-chain PFCAs exceeded PFOA levels in serum. Among these PFCAs, perfluoroundecanoic acid (PFUnDA) was the predominant component (28.5%), followed by perfluorononanoic acid (PFNA 17.5%), perfluorodecanoic acid (PFDA 7.9%), perfluorotridecanoic acid (PFTrDA 6.1%) and perfluorododecanoic acid (PFDoDA 1.8%). Odd-numbered PFCAs (PFNA, PFUnDA and PFTrDA) were also observed in Korea and Vietnam and their presence increased significantly in Korea between 1994 and 2007/2008. The proportion of long-chain PFCAs in serum was relatively high compared to reports in Western countries. Further investigations into the sources and exposure routes are needed to predict the future trajectory of these serum PFCA levels.     

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.     

Effect of seepage conditions on chemical attenuation of arsenic by soils across an abandoned mine site

The effect of seepage velocity on the As leaching/adsorption by soils collected from abandoned mine sites was evaluated under batch equilibrium and different seepage settings. The breakthrough curves (BTCs) of As leaching from the mine soil column initially displayed the peak export and gradually leveled off over the leaching experiment. A similar As peak was observed after a flow interruption period. Adsorption by downgradient soils was clearly nonlinear, as Freundlich N was <1. In the BTCs of the layered columns, where downgradient soils were overloaded above the mine soil, the extended lag period of As appearance and lower steady-state As concentration observed for slow seepage velocity supported the idea of kinetically limited As attenuation driven by soil adsorption. The perturbation of As concentration was insignificant when the intra-column As concentration gradient was higher. The As concentration drop and time to recovery were greater for less adsorptive soil and fast seepage velocity. Desorption of As from soils retrieved from both batch adsorption and column experiment demonstrate hysteric behavior. The results of this work demonstrated that the risk of As leaching from an abandoned mine site can be greatly attenuated by intermediate downgradient soils via chemical adsorption, which tends to be kinetically limited and energetically hysteric (i.e., non-identical energy pathway).     

Heavy metal immobilization in soil near abandoned mines using eggshell waste and rapeseed residue

Heavy metal contamination of agricultural soils has received great concern due to potential risk to human health. Cadmium and Pb are largely released from abandoned or closed mines in Korea, resulting in soil contamination. The objective of this study was to evaluate the effects of eggshell waste in combination with the conventional nitrogen, phosphorous, and potassium fertilizer (also known as NPK fertilizer) or the rapeseed residue on immobilization of Cd and Pb in the rice paddy soil. Cadmium and Pb extractabilities were tested using two methods of (1) the toxicity characteristics leaching procedure (TCLP) and (2) the 0.1 M HCl extraction. With 5 % eggshell addition, the values of soil pH were increased from 6.33 and 6.51 to 8.15 and 8.04 in combination with NPK fertilizer and rapeseed residue, respectively, compared to no eggshell addition. The increase in soil pH may contribute to heavy metal immobilization by altering heavy metals into more stable in soils. Concentrations of TCLP-extracted Cd and Pb were reduced by up to 67.9 and 93.2 % by addition of 5 % eggshell compared to control. For 0.1 M HCl extraction method, the concentration of 0.1 M HCl-Cd in soils treated with NPK fertilizer and rapeseed residue was significantly reduced by up to 34.01 and 46.1 %, respectively, with 5 % eggshell addition compared to control. A decrease in acid phosphatase activity and an increase in alkaline phosphatase activity at high soil pH were also observed. Combined application of eggshell waste and rapeseed residue can be cost-effective and beneficial way to remediate the soil contaminated with heavy metals.     

Phytotoxicity and phytoremediation of 2,6-dinitrotoluene using a model plant, Arabidopsis thaliana

Biochemical and genetic studies of xenobiotic metabolism in the model plant Arabidopsis have significant potential in providing information for phytoremediation. This paper presents the toxicity of 2,6-dinitrotoluene (2,6-DNT) to Arabidopsis under axenic conditions, the fate and transformation of 2,6-DNT after uptake by the plant, and the effect of a putative glutathione S-transferase (GST), which is highly induced by 2,4,6-trinitrotoluene (TNT) in the previous study, on the detoxification of 2,6-DNT. 2,6-DNT had toxic effects on the growth of Arabidopsis based on whole seedling as well as root growth assays. Using [U- 14C]2,6-DNT, the recovery was over 87% and less than 2% accounted for the mineralization of 2,6-DNT in axenic liquid cultures during the 14d of exposure. About half (48.3%) of the intracellular radioactivity was located in the root tissues in non-sterile hydroponic cultures. 2-Amino-6-nitrotoluene (2A6NT) and two unknown metabolites were produced as transformation products of 2,6-DNT in the liquid media. The metabolites were further characterized by proton NMR spectra and the UV-chromatograms when the plant was fed with either 2,6-DNT or 2A6NT. In addition, polar unknown metabolites were detected at short retention times from radiochromatograms of plant tissue extracts. The GST gene of the wild-type of Arabidopsis in response to 2,6-DNT was induced by 4.7-fold. However, the uptake rates and the tolerance at different concentrations of 2,6-DNT and TNT were not significantly different between the wild-type and the gst mutant indicating that induction of the GST gene is not related to the detoxification of 2,6-DNT.     

Environmental and economic feasibility study of a total wastewater treatment network system

The synthesis of distributed wastewater treatment plants (WTPs) has been studied to reduce capital and operating costs associated with wastewater treatment. In this study, the environmental and economic feasibility of a total wastewater treatment network system (TWTNS) including distributed and terminal WTPs was estimated using life cycle assessment (LCA) and life cycle costing (LCC) methods. Wastewater sources and existing distributed and terminal WTPs in an iron and steel plant were networked. The TWTNS was generated from the optimal solution to a mathematical optimization model and compared to a conventional wastewater treatment system (CWTS). The environmental effect scores of the TWTNS were from 29.6% to 68.3% higher than those of the CWTS because of higher electricity consumption required to pump wastewater to the networked WTPs. However, the life cycle cost of the TWTNS was lower than that of the CWTS by 10.1% because of the decrease of the labor cost resulting from the closing of three distributed WTPs. Overall, the TWTNS was no more eco-efficient than the CWTS because the increase of environmental burdens outweighed the decrease of economic costs.     

Leaching mechanisms of Cr(VI) from chromite ore processing residue

Batch leaching tests, qualitative and quantitative x-ray powder diffraction (XRPD) analyses, and geochemical modeling were used to investigate the leaching mechanisms of Cr(VI) from chromite ore processing residue (COPR) samples obtained from an urban area in Hudson County, New Jersey. The pH of the leaching solutions was adjusted to cover a wide range between 1 and 12.5. The concentration levels for total chromium (Cr) and Cr(VI) in the leaching solutions were virtually identical for pH values >5. For pH values <5, the concentration of total Cr exceeded that of Cr(VI) with the difference between the two attributed to Cr(III). Geochemical modeling results indicated that the solubility of Cr(VI) is controlled by Cr(VI)-hydrocalumite and Cr(VI)-ettringite at pH >10.5 and by adsorption at pH <8. However, experimental results suggested that Cr(VI) solubility is controlled partially by Cr(VI)-hydrocalumite at pH >10.5 and by hydrotalcites at pH >8 in addition to adsorption of anionic chromate species onto inherently present metal oxides and hydroxides at pH <8. As pH decreased to <10, most of the Cr(VI) bearing minerals become unstable and their dissolution contributes to the increase in Cr(VI) concentration in the leachate solution. At low pH ( <1.5), Cr(III) solid phases and the oxides responsible for Cr(VI) adsorption dissolve and release Cr(III) and Cr(VI) into solution.     

Chlorinated, brominated, and perfluorinated compounds, polycyclic aromatic hydrocarbons and trace elements in livers of sea otters from California, Washington, and Alaska (USA), and Kamchatka (Russia)

Concentrations of organochlorine pesticides (DDTs, HCHs, and chlordanes), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), perfluorinated compounds (PFCs), and 20 trace elements were determined in livers of 3- to 5-year old stranded sea otters collected from the coastal waters of California, Washington, and Alaska (USA) and from Kamchatka (Russia). Concentrations of organochlorine pesticides, PCBs, and PBDEs were high in sea otters collected from the California coast. Concentrations of DDTs were 10-fold higher in California sea otters than in otters from other locations; PCB concentrations were 5-fold higher, and PBDE concentrations were 2-fold higher, in California sea otters than in otters from other locations. Concentrations of PAHs were higher in sea otters from Prince William Sound than in sea otters from other locations. Concentrations of several trace elements were elevated in sea otters collected from California and Prince William Sound. Elevated concentrations of Mn and Zn in sea otters from California and Prince William Sound were indicative of oxidative stress-related injuries in these two populations. Concentrations of all of the target compounds, including trace elements, that were analyzed in sea otters from Kamchatka were lower than those found from the US coastal locations.     

Preparation of a highly sensitive enzyme electrode using gold nanoparticles for measurement of pesticides at the ppt level

A highly sensitive enzyme electrode was prepared based on gold nanoparticles for measurement of pesticides. Gold nanoparticles of 25-30 nm were synthesized on a glassy carbon electrode by double-pulse technique while the coverage was controlled by applied potential and time. The gold nanoparticles were modified to form a self-assembled monolayer, followed by covalent binding of tyrosinase. The TYR-AuNP-GC electrode was compared with bare GC, AuNP-GC, and modified AuNP-GC and TYR-Au (plate type) electrodes in terms of cyclic voltammetry. The voltammograms well represent the sensitivity of enzymatic oxidation of catechol, substrates for the enzyme activity. The prepared electrode integrated into a continuous flow system and was tested to detect pesticides, such as 2,4-D, atrazine, and ziram. Under the optimized conditions of the flow system, the electrode performed reasonably according to the inhibition mechanism in the concentration range of 0.001-0.5 ng mL(-1). The enhanced performance was attributed to the favored microenvironment for the enzyme activity provided by SAM on gold nanoparticles.