Assessment of fates of estrogens in wastewater and sludge from various types of wastewater treatment plants

We measured five estrogens in the wastewater samples from the municipal wastewater treatment plants (M-WWTPs), livestock wastewater treatment plants (L-WWTPs), hospital WWTPs (H-WWTPs) and pharmaceutical manufacture WWTPs (P-WWTPs) in Korea. The L-WWTPs showed the highest total concentration (0.195-10.4 μg L⁻¹) of estrogens in the influents, followed by the M-WWTPs (0.028-1.15 μg L⁻¹), H-WWTPs (0.068-0.130 μg L⁻¹) and P-WWTPs (0.015-0.070 μg L⁻¹). Like the influents, the L-WWTPs (0.003-0.729 μg L⁻¹) and the M-WWTPs (0.001-0.299 μg L⁻¹) also showed higher total concentration of estrogens in the effluents than the H-WWTPs (0.002-0.021 μg L⁻¹) and P-WWTPs (0.011 μg L⁻¹ in one sample). The L-WWTPs (37.5-543 μg kg⁻¹, dry weight) showed higher total concentrations in sludge than the M-WWTPs (3.16-444 μg kg⁻¹, dry weight) like the wastewater. The distribution of estrogens in the WWTPs may be affected by their metabolism in the human body, their transition through biological treatment processes, and their usage for livestock growth. Unlike the concentration results, the daily loads of estrogens from the M-WWTPs were the highest, which is related to the high capacities of WWTPs.     

Nationwide monitoring of atmospheric PCDD/Fs and dioxin-like PCBs in South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured in ambient air samples collected from different parts of South Korea in 2008, and the measured levels were used for assessing the spatial and temporal distribution of atmospheric PCDDFs and DL-PCBs in South Korea. The average concentrations of atmospheric PCDD/Fs and DL-PCBs among the 37 sites were 28 fg I-TEQ m⁻³ (ND ∼ 617) and 1 fg WHO-TEQ m⁻³ (ND ∼ 0.016). Elevated atmospheric levels of PCDD/Fs and DL-PCBs observed at residential/industrial sites and in the north-west of Korea, indicated a potential contribution and impacts of anthropogenic sources of PCDD/Fs and DL-PCBs. These levels were similar or lower than those previously reported in other ambient air surveys. Average concentrations of PCDD/Fs showed small seasonal variations (ANOVA analysis, p = 0.144). The highest concentrations of PCDD/Fs were observed during winter, followed by spring, autumn and summer. Atmospheric PCDD/Fs and DL-PCBs in South Korea rapidly decreased during the last 10 years (1998-2008), demonstrating the efficiency of stricter regulations and the application of best available technologies/best environmental practices at emission sources. Comparison of the congener profiles and principal component analysis showed that current atmospheric PCDD/Fs are mostly influenced by industrial sources and PCBs from old commercial PCB uses. Nationwide POPs monitoring will continue and allows an effective evaluation of the implementation of the Stockholm Convention on POPs.     

Use of reporter-gene based bacteria to quantify phenanthrene biodegradation and toxicity in soil

A phenanthrene-degrading bacterium, Sphingomonas paucimobilis EPA505 was used to construct two fluorescence-based reporter strains. Strain D harboring gfp gene was constructed to generate green fluorescence when the strain started to biodegrade phenanthrene. Strain S possessing gef gene was designed to die once phenanthrene biodegradation was initiated and thus to lose green fluorescence when visualized by a live/dead cell staining. Confocal laser scanning microscopic observation followed by image analysis demonstrates that the fluorescence intensity generated by strain D increased and the intensity by strain S decreased linearly at the phenanthrene concentration of up to 200 mg/L. Such quantitative increase and decrease of fluorescence intensity in strain D (i.e., from 1 to 11.90 ± 0.72) and strain S (from 1 to 0.40 ± 0.07) were also evident in the presence of Ottawa sand spiked with the phenanthrene up to 1000 mg/kg. The potential use of the reporter strains in quantitatively determining biodegradable or toxic phenanthrene was discussed.     

Molecular cloning and expression of novel metallothionein (MT) gene in the polychaete Perinereis nuntia exposed to metals

To report a novel metallothionein (MT) gene and evaluate its potency as a biomarker, we clone this MT gene and measured the expression levels in the metal-exposed polychaete Perinereis nuntia. Accumulated metal contents and metallothionein-like proteins (MTLPs), which have been recognized as potential biomarkers, were compared with the relative mRNA expressions of the MT gene of P. nuntia (Pn-MT). In addition, the metal-binding affinity was estimated by recombinant Pn-MT protein. Pn-MT having high cysteine residues with three metal response elements in the promoter region closely clusters with those of other invertebrates. The accumulation patterns of metals were dependent on the exposure times in lead (Pb), cadmium (Cd), and copper (Cu) exposure. Particularly, both MTLP levels and relative mRNA expressions of MT were increased with accumulated metal contents and exposure time in P. nuntia exposed to Pb and Cd. There was no significant modulation of the Pn-MT gene in polychaetes exposed to Zn and As. However, the metal-binding ability of the recombinant Pn-MT protein provides a clear evidence for a high affinity of MT to several metal elements. These results suggest that Pn-MT would play an important role in the detoxification and/or sequestration of specific metals (e.g., Pb and Cd) in P. nuntia and have potential as a molecular biomarker in the monitoring of the marine environment using a polychaete.     

Induced anti-predator responses of the green mussel, Perna viridis (L.), on exposure to the predatory gastropod, Thais clavigera Küster, and the swimming crab, Thalamita danae Stimpson

A laboratory experiment was conducted to test whether anti-predator responses could be induced in the green mussel, Perna viridis, on exposure to waterborne cues from two predators, the muricid gastropod, Thais clavigera, and the portunid crab, Thalamita danae, and from damaged conspecifics. There were five treatments in this study. Aquaria of two treatments housed either Thalamita danae or Thais clavigera. Another three treatments housed only intact mussels, broken and intact mussels, or no mussels. No significant differences were found among these five treatments in final shell weight and tissue dry weight. Induced defensive responses were predator-specific. Experimental mussels exposed to waterborne cues of T. clavigera had a higher percentage increase in shell length, height and width, whereas those exposed to waterborne cues of T. danae had a higher percentage increase in shell width and height. Mussels raised in the presence of crabs developed thicker shell at the umbo and lip margin, whereas mussels raised in the presence of gastropods had thicker shell lip. Predator preference for mussels from the control group and for those pre-exposed to waterborne cues of either of the predators was studied. T. clavigera preferentially selected mussels from the control group, whereas no prey preference was found for T. danae, although shell breaking time for mussels exposed to a crab was longer than that for the control. While the present results should be viewed with caution in the absence of a dietary control, this was the first time that prey handling was shown to be affected by defensive changes in the morphology of mussels.Communicated by T. Ikeda, Hakodate     

Polychlorinated dibenzo-p-dioxins and dibenzofurans from food salt samples processed by heat treatment in Korea

Eight samples of processed food salt collected from five plants in Korea were analyzed for 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) using liquid-liquid extraction, clean-up procedures, and high resolution gas chromatography-high resolution mass spectrometry. The study included the analyses of two kinds of salt product sample: bamboo-salt and parched salt. The levels of toxic PCDD/Fs found in the salt product samples were extremely low: the results revealed TEQ levels ranging between the sub pg TEQ/g and sub fg TEQ/g. The differences in the TEQ values of toxic PCDD/F were observed between the salt product samples, which were treated with different frequency of baking using four different fuels (firewood, pine wood, pine resin, and indirect heating by gas) at temperatures from 300 to 2000 degrees C. In bamboo-salt samples, the concentrations and TEQ values of toxic PCDD/Fs ranged between 0.57-66 pg/g and 5.7x10(-5)-0.64 pg TEQ/g, respectively. PCDD/Fs levels in bamboo-salts baked by firewood were found to be higher than those baked by pinewood or pine resin. In parched salt samples, the concentrations and TEQ values of toxic PCDD/Fs ranged between 0.97-3.7 pg/g and 0.0097-0.017 pg TEQ/g, respectively. The data was discussed regarding the concentration and the distribution pattern of congeners.     

Effects of basic oxygen furnace slag and inorganic nutrients on the germination of resting cysts of two toxic dinoflagellates

Effects of basic oxygen furnace (BOF) slag, inorganic nutrients and H2S on the germination of resting cysts of two toxic dinoflagellates Alexandrium catenella/tamarense and Gymnodinium catenatum were studied in batch cultures. The germination rate of the test species has increased by 23-25%, when the concentration of NO3--N or H2S in culture medium has increased to 2.0 ppm. At the treatment of enriched NH4+-N and PO43--p, the germination of resting cyst was increased. Nevertheless, the increased range in germination rates was less than those of NO3--N and H2S. When BOF slag in culture medium increased to 50 mg/ml (or 500 g/m2), the cyst germination rate fell to less than 5%. At higher level of concentrations germination was completely inhibited. Adding BOF slag to the culture medium reduced the concentration of inorganic salts and H2S in seawater and sediments, resulting in the inhibition of cyst germination. These findings demonstrate the potential use of BOF slag on the sediments seed bank of red tide organism because it has an ability to inhibit resting cysts germination.     

Improvement of thermal hydrolysis rate of dichloroacetic acid using alcohol

Dichloroacetic acid (DCAA) is produced during the oxidation of trichloroethylene. It is also produced in drinking water treatment as a disinfection by-product. DCAA is a problem material, because of its toxicity. The objective of this research is to find the final products and the reaction pathway of the DCAA decomposition by hydrolysis, and to increase the hydrolysis rate. The removal of both chlorine atoms in DCAA structure was achieved with hydrolysis at around 75 degrees C, and the final products were oxalic acid and glycolic acid. The reaction pathway was the production of oxalic acid and glycolic acid from two glyoxylic acid molecules by Cannizzaro reaction after the glyoxylic acid production from dechlorination of DCAA with hydrolysis. The hydrolysis rate of DCAA was increased with the use of 90% ethanol solution as solvent. The activation energy of DCAA was about 80 kJ/mol in it, while it was around 105 kJ/mol in water.     

Benefits-based analysis of visitor use of Sorak-san National Park in Korea

Benefits-based management seeks to provide recreation benefits for recreation participants by managing the physical environments in which recreation occurs. This study investigates the relationship between benefits desired by visitors and the physical, social, and managerial characteristics of settings that facilitate realization of recreation benefits. Data such as perceived benefits from recreation experiences, setting attributes that significantly influenced perceived benefits, and sociodemographic variables were collected from 376 visitors to Sorak-san National Park in the eastern part of the Korean peninsula. Cluster analysis was used to group visitors' desired benefits into 12 domains: relationship with nature/scenery, escaping pressure, learning about nature, family togetherness, introspection, exploration, autonomy/achievement, being with friends, leading others, skills/learning, risk taking, and meeting/observing new people. Multiple regression was used to link benefit domains with the characteristics of settings. The social attribute of recreation settings was linked to eight of the ten benefit domains. There were two statistically strong multiple regression correlations: (1) between domain of “relationship with nature /scenery” and the attributes “forest/water,”“attractive nature,” and “facility/maintenance” and (2) between the domain of “escaping pressure” and the attributes “attractive nature” and “social.” The results of this study are useful to managers in their efforts to provide recreation opportunities for visitors to achieve beneficial outcomes.