Development of freshwater sediment management standards for organic matters, nutrients, and metals in Korea

Korean water quality managers are required to promptly develop national assessment standards for freshwater sediment quality due to the Four Major River Restoration Project in Korea in 2009. We conducted this study to develop sediment management standards (SMSs), determining obviously and severely polluted sediment, which could have adverse impacts on water quality and aquatic ecosystem. The SMSs values were derived from the 95th percentile of concentration distribution for organic matter and nutrients in sediment quality database. For the SMSs of metals, foreign sediment quality guidelines (SQGs) were adopted. As a result, 13 % for loss on ignition (LOI), 1,600 mg/kg for total phosphorus (TP), and 5,600 mg/kg for total nitrogen (TN) were set as the SMSs for freshwater sediment in Korea. These values were higher than the range of heavily polluted sediment from USEPA Region 5 guideline derived by the similar approaches for the Great Lakes harbor sediments, and similar or lower than the severe effect level (SEL) from provincial sediment quality guideline (PSQG) of Ontario, Canada by screening level concentration (SLC) approach. However, SMSs in the present study are appropriate considering the concentration ranges and the Korean SMSs’ definition for freshwater sediments in Korea. The Puget Sound marine sediment cleanup screening level (CSL) in Washington State, USA were adopted as the Korean SMSs for As (93 mg/kg), Cd (6.7 mg/kg), Cr (270 mg/kg), Cu (390 mg/kg), Pb (530 mg/kg), and Zn (960 mg/kg) in freshwater sediments. Hg concentration (0.59 mg/kg) of CSL was too low to determine the polluted freshwater sediments in Korea, and the SEL of Ontario, Canada for mercury concentration (2 mg/kg) was selected as the SMS for Hg. These values were found reasonable through the assessment of applicability with the datasets from locations directly affected by obvious point sources. These results indicate that SMSs for organic matter, nutrient, and metals derived within the present study can successfully determine obviously and severely polluted sediment in Korea. However, the SMSs have limits to specifically determine the effects of polluted sediment on water quality and aquatic ecosystem in Korea. Thus, we will revise and specify SMSs considering those effects and further sediment quality assessment framework in the near future.     

Microbial degradation of dissolved organic matter (DOM) and its influence on phenanthrene-DOM interactions

Microbial degradation-induced changes in the characteristics of dissolved organic matter (DOM), and the subsequent effects on phenanthrene-DOM interactions were investigated based on the microbial incubation of DOM collected from four different sources for 28 d. Partially biodegraded DOM presented higher specific UV absorbance (SUVA), lower protein-like fluorescence, higher humic-like fluorescence, lower aliphatic carbon fraction, and higher hydrophobic neutral fractions compared to the original DOM. Microbial changes in DOM led to an increase in the isotherm nonlinearity as well as the extent of phenanthrene binding. A negative relationship between SUVA and the Freundlich n values was established for the original and the biodegraded DOM, suggesting that aromatic condensed structures may play important roles in providing nonlinear strong binding sites irrespective of microbial degradation. In contrast, there were two separate slopes of the correlations between the percentage of hydrophobic acid (HoA) fraction and the n values for the original and the biodegraded DOM with a higher slope exhibited for the latter, implying that the microbial utilization of oxygen-containing structures in the HoA fractions may contribute to enhancing the associated isotherm nonlinearity.     

Cadmium ion sorption onto lignocellulosic biosorbent modified by sulfonation: the origin of sorption capacity improvement

Juniper (Juniperus monosperma), a small-diameter underutilized material, has been studied as a lignocellulosic biosorbent for removing heavy metals from water. In this study, juniper wood was modified by sulfonation to enhance sorption capacity for cadmium in water. The origin of the enhancement was investigated by observing the sorption behaviors and the change in surface functional group concentrations. Cadmium sorption by all juniper wood biosorbents studied was fast and the sorption capacity decreased with decreasing pH, similar to results found for other biosorbents. Sulfonated juniper was found to have at least twice the sorption capacity for cadmium removal from water compared to that of untreated juniper, though the sorption capacity increased with increasing pH. A slight increase in carboxylate content after sulfonation was likely responsible for a small portion of the enhancement. Elemental analysis showed an increase in sulfur content after sulfonation. Diffuse reflectance infrared Fourier transform (DRIFT) spectra showed a decrease in the band at 1660 cm(-1) in the range of carbonyl groups as a result of sulfonation. This indicates that coniferaldehyde groups in the lignin of juniper wood corresponding to this band were substituted into sulfonic acid groups after sulfonation. This interpretation was supported by both the color forming reaction with phloroglucinol-hydrochloric acid and the reaction mechanisms from the acid sulfite pulping process. Consequently, the enhancement of cadmium sorption capacity of juniper wood by sulfonation mainly originated from the production of sulfonic acid groups, which are binding sites for heavy metals.     

APPLICATION OF THE GENETIC ALGORITHM FOR OPTIMIZING OPERATION RULES OF THE LiYuTan RESERVOIR IN TAIWAN1

ABSTRACT: A procedure to apply genetic algorithm to optimize operation rules is proposed and applied to the LiYuTan Reservoir in Taiwan. The designed operation rules are operation zones with discount rates of water supply. The first step of the procedure is to predefine the shape of boundary curves of operation zones according to reservoir storage routing. Then, relatively fewer variables are used to describe the curves, and a last genetic algorithm (GA) is applied to optimize the curves. The procedure is applied to the newly built LiYuTan Reservoir for increasing domestic water demands. Shortage index is used to evaluate the performance of operation zones. A year is divided into 36 operational periods, with each month containing three operational periods. The shortage indexes calculated in operational periods are 9.81, 8.27, and 7.13, respectively, for the reservoir without operation rules, applying operation zones optimized by GA with encoding 36 storage levels for each curve, and adopting operation zones optimized by GA with encoding the curves with predefined shape. The average deficits for the three cases are 77.2, 43.6, and 33.3 (10⁴ m³/day), respectively. The results indicate that operation zones optimized by the proposed procedure have smaller shortage indexes and lower average deficits. In addition, the optimized operation zones have less variation and thus are more practical for operation. Conclusively, the proposed procedure utilizing GA to optimize operation zones with predefined shape can provide better and realistic outcomes through limited iterations.     

SPATIAL VARIABILITY OF CONDUCTWITY AS APPLIED TO DISTRIBUTED PARAMETER INFILTRATION MODELS1

ABSTRACT: Two infiltration models, called VVSIM (variable variance stochastic infiltration model) and EVVSIM (enhanced variable variance stochastic infiltration model), are developed in this study. A distributed parameter infiltration model can estimate the amount of infiltration over a field area by computing the infiltration over zones of the field area. Hydraulic conductivity is the most important parameter determining infiltration in simulations by infiltration models. The performance of an infiltration model depends on how well the model accommodates the complicated spatial distribution of hydraulic conductivity. The two proposed models include the effects of spatial correlation of the conductivity distribution. Virtual conductivity fields are generated using the turning bands method. Monte Carlo simulations show that the proposed models give infiltration estimates more accurate than those obtained by the other models employed.     

Use of two population metrics clarifies biodiversity dynamics in large-scale monitoring: the case of trees in Japanese old-growth forests

An alkaline comet assay and a micronucleus test were carried out on erythrocytes of the European chub, Squalius cephalus L., collected in spring and autumn in 2005 and 2006 at three sampling sites in River Sava, near Zagreb, Croatia. The results of comet assay showed the lowest genotoxic influence at the least polluted site, while higher DNA damage was observed at the polluted sites. Although the basal levels of DNA damage were elevated, a clear gradation of DNA damage was found due to pollution intensity in all sampling periods. The lowest cytogenetic damage as revealed by the micronucleus test (MNT) was observed as well at the least polluted site. High variations in MN frequency were observed between sampling periods, although the number of micronucleated erythrocytes was consistently the highest one at the polluted site. The comet assay as a biomarker of genotoxic effect exhibited higher sensitivity in discriminating the genotoxic capacity of studied polluted sites while the MNT was less sensitive. However, both tests should be used together in biomonitoring studies because they can reveal different aspects of DNA damage; comet assay, the early event of genotoxic exposure, and MNT, its final result as a mutagenic potential.     

Brominated flame retardants in the environment of Asia-Pacific: an overview of spatial and temporal trends

In this paper, we summarize spatial and temporal trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in coastal and marine biota, and further assess human exposure to these brominated flame retardants (BFRs) in Asia-Pacific. The review is based mainly on the studies that were conducted in our laboratory and utilized samples archived in the environmental specimen bank (es-BANK) of Ehime University, Japan. The studies suggest that the target BFRs are ubiquitous in the environment of Asia-Pacific. Examination of spatial trends reveals that concentrations of these contaminants are relatively high in samples from Korea, South China and Japan. In general, the magnitude of environmental contamination by PBDEs in Asia-Pacific, as well as human exposure to these contaminants, seem to be comparable to or slightly higher than in Europe, but lower than in North America. Evaluation of temporal trends in concentrations of BFRs in marine mammals from the coastal waters of Japan and China showed drastic increase during the last 30 years. These changes in BFR levels in samples from Japan were in line with trends in production/use of the commercial formulations. Since the withdrawal of some PBDE products from the Japanese market in the 1990s, concentrations of HBCDs appear to exceed those of PBDEs, reflecting increasing usage of HBCDs over PBDEs. The increasing environmental contamination by BFRs in Chinese coastal waters indicates that contamination by BFRs has already become evident, even in developing countries. In view of the rising environmental levels and the high consumption volume of BFRs in Asia, further efforts should be made to monitor environmental contamination by these chemicals in order to identify sources and reduce emissions.     

Degradation pathways of decabromodiphenyl ether during hydrothermal treatment

The hydrothermal degradation pathways of decabromodiphenyl ether during hydrothermal treatment were investigated. After an initial "Heating time", the reaction runs were carried out at constant temperature (heating to 300 degrees C and keeping temperature) and pressure (8MPa) in a SUS316 stainless steel micro autoclave filled with water. Some decomposition of decabromodiphenyl ether was observed over 200 degrees C, and it was decomposed by more than 99% after 10 min at 300 degrees C. The reactivities of bromine on para and meta substituents were relatively high, while its reactivity on ortho bromine was extremely low. The formations of polybrominated dibenzo-p-dioxins and furans (PBDD/DFs) were observed in the early stages of the reactions at around 300 degrees C. The TCDD toxicity equivalency (TCDD-EQs) of the by-products was determined based on relative potencies (REPs EC(5TCDD)) with the Dioxin-Responsive-Chemical Activated Luciferase gene eXpression (DR-CALUX) bioassays technology. These results indicated that the risk of formation of PBDD/DFs in the hydrothermal degradation of deca-BDE was low, and it would be possible to reduce the TCDD-EQs value by adding some catalyst or alkali, or extending processing time.