Hyun-Sang Shin

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.

Estimating the Concentration and Biodegradability of Organic Matter in 22 Wastewater Treatment Plants Using Fluorescence Excitation Emission Matrices and Parallel Factor Analysis

This study aimed at monitoring the changes of fluorescent components in wastewater samples from 22 Korean biological wastewater treatment plants and exploring their prediction capabilities for total organic carbon (TOC), dissolved organic carbon (DOC), biochemical oxygen demand (BOD), chemical oxygen demand (COD), and the biodegradability of the wastewater using an optical sensing technique based on fluorescence excitation emission matrices and parallel factor analysis (EEM-PARAFAC). Three fluorescent components were identified from the samples by using EEM-PARAFAC, including protein-like (C1), fulvic-like (C2) and humic-like (C3) components. C1 showed the highest removal efficiencies for all the treatment types investigated here (69% ± 26%–81% ± 8%), followed by C2 (37% ± 27%–65% ± 35%), while humic-like component (i.e., C3) tended to be accumulated during the biological treatment processes. The percentage of C1 in total fluorescence (%C1) decreased from 54% ± 8% in the influents to 28% ± 8% in the effluents, while those of C2 and C3 (%C2 and %C3) increased from 43% ± 6% to 62% ± 9% and from 3% ± 7% to 10% ± 8%, respectively. The concentrations of TOC, DOC, BOD, and COD were the most correlated with the fluorescence intensity (Fmax) of C1 (r = 0.790–0.817), as compared with the other two fluorescent components. The prediction capability of C1 for TOC, BOD, and COD were improved by using multiple regression based on Fmax of C1 and suspended solids (SS) (r = 0.856–0.865), both of which can be easily monitored in situ. The biodegradability of organic matter in BOD/COD were significantly correlated with each PARAFAC component and their combinations (r = −0.598–0.613, p < 0.001), with the highest correlation coefficient shown for %C1. The estimation capability was further enhanced by using multiple regressions based on %C1, %C2 and C3/C2 (r = −0.691).

Comparison of the characteristics of extracellular polymeric substances for two different extraction methods and sludge formation conditions

The characteristics of extracellular polymeric substances (EPSs) were compared for two different extraction methods and dissimilar sludge formation conditions (aerobic versus anaerobic). The measured characteristics included specific ultraviolet absorbance (SUVA) values, fluorescence excitation-emission matrices, molecular weight distributions, Fourier transform infrared (FT-IR) spectra, and the binding affinities for pyrene and Hg(II). The analyses demonstrated that the EPS extracted using cation exchange resin (CER) were composed of more aromatic and more condensed structures with higher molecular weight than those using formaldehyde/NaOH. The FT-IR results further revealed that the EPS using CER contained relatively lower content of protein to carbohydrate and less acidic functional groups (i.e., COOH or OH groups). The observed differences between the two extraction methods were more pronounced for the EPS of anaerobic sludge compared to those of aerobic sludge. The extent of pyrene binding and the apparent stability constants for Hg(II) were very consistent with the implications from the previous EPS physicochemical characteristics. The highest extent of pyrene binding was observed for the EPS of anaerobic sludge using CER while no measurable Hg(II) stability constant was found for the same EPS sample. Our results demonstrated that the EPS characteristics including their binding affinities are likely strongly affected by the sludge formation conditions as well as the extraction methods although the latter produced more differences.

Dynamics of dissolved organic matter during four storm events in two forest streams: source, export, and implications for harmful disinfection byproduct formation

Dynamics of river dissolved organic matter (DOM) during storm events have profound influences on the downstream aquatic ecosystem and drinking water safety. This study investigated temporal variations in DOM during four storm events in two forest headwater streams (the EH and JH brooks, South Korea) and the impacts on the disinfection byproducts (DBPs) formation potential. The within-event variations of most DOM quantity parameters were similar to the flow rate in the EH but not in the larger JH brook. The dissolved organic carbon (DOC) showed clockwise and counterclockwise hysteresis with the flow rate in the EH and JH brooks, respectively, indicating the importance of both flow path and DOM source pool size in determining the effects of storm events. The stream DOM became less aromatic/humified from the first to the last event in both brooks, probably due to the increasing fresh plant pool and the decreasing leaf litter pool during the course of rainy season. The DOC export during each event increased 1.3–2.7- and 1.1–7.0-fold by stormflows in the EH and JH brooks, respectively. The leaf litter and soil together was the major DOM source, particularly during early events. The enhanced DOM export probably increases the risks of DBPs formation in disinfection, as indicated by a strong correlation observed between DOC and trihalomethanes formation potential (THMFP). High correlations between two humic-like fluorescent components and THMFP further suggested the potential of assessing THMFP with in situ fluorescence sensors during storms.

Seasonal and storm-driven changes in chemical composition of dissolved organic matter: a case study of a reservoir and its forested tributaries

Many drinking water supplies are located in forested watersheds, which operate as an important source of dissolved organic matter (DOM). In this study, monthly sampling campaigns were conducted from a reservoir (Daecheong Reservoir, South Korea) and its forested tributaries for five consecutive months (June to October) to examine the variations of DOM composition. Excitation-emission matrix fluorescence spectroscopy combined with parallel factor analysis (EEM-PARAFAC) was applied to track the variations of different fluorescent components within bulk DOM. Selected samples were further separated into hydrophobic (Ho) and hydrophilic (Hi) fractions. Water quality and DOM composition varied greatly with the sampling locations including the upstream and the downstream tributary sites, and the reservoir. Non-metric multidimensional scaling (NMDS) provided the information on the DOM sources and the potential processes leading to the observed DOM changes. Four of the five fluorescent components, identified by EEM-PARAFAC, were well correlated with the flow rates of the tributaries, suggesting hydrological control on DOM composition. The greatest effects were found on two terrestrial humic-like components (C1 and C2). The Ho fraction of DOM was more abundant for the post-storm samples versus the non-storm samples, supporting the important roles of hydrology on the changes in chemical composition of DOM. The amounts of the DOM resin fractions, either Ho or Hi, showed strong relationships with C1 and C2, suggesting that DOM fluorescence could be successfully applied to estimate different DOM chemical constituents in forested watersheds.

Correlation of Heavy Metal Concentrations between Total Digestion and Aqua Regia Digestion for Sediments from Yeongsan and Seomjin Watersheds

In this study, the correlations of concentrations in sediment heavy metals between two pretreatment methods, total digestion and aqua regia digestion, have been investigated. Total 43 samples had been collected from streams and lakes in Yeongsan and Seomjin watersheds. They were decomposed in two pretreatment methods and five metal components (Cd, Cr, Ni, Pb, Zn) were analyzed. Overall average concentrations of heavy metals were Zn>Cr>Pb>Ni>Cd in the order. The concentrations of aqua regia digestion were 35.0% (Cd), 53.8% (Cr), 66.2% (Ni), 64.4% (Pb) and 76.4% (Zn) of the concentrations of total digestion and heavy metal concentrations of total digestion were higher. Heavy metal concentrations in sediments from lakes were higher than those from streams. The correlation equations between the concentrations of total digestion and aqua regia digestion were obtained. The concentrations of Zn and Ni, which showed strong linear correlations, increased in aqua regia digestion as the concentration in total digestion increased. The linear correlation coefficients between two digestion methods for most analyzed metals were above the average correlation. However, these results can be applied with limitations due to heterogeneity of sediments.

Influences of Environmental Conditions and Refractory Organic Matters on Organic Carbon Oxidation Rates Measured by a High Temperature Combustion and a UV-sulfate Methods

This study examined the effects of environmental conditions and the presence of refractory organic matter on oxidation rates of total organic carbon (TOC) measurements based on high temperature combustion and ultraviolet-sulfate methods. Spectroscopic indices for prediction of oxidation rates were also explored using the UV spectra and fluorescence excitation- emission matrix (EEM) of humic acids. Furthermore, optimum TOC instrument conditions were suggested by comparing oxidation rates of a standard TOC material under various conditions. Environmental conditions included salts, reduced ions, and suspended solids. Salts had the greatest influence on oxidation rates in the UV-sulfate method. However, no effect was detected in the high temperature combustion method. The UV-sulfate method showed lower humic substance oxidation rates, refractory natural organic matter, compared to the other methods. TOC oxidation rates for the UV-sulfate method were negatively correlated with higher specific-UV absorbance, humification index, and humic-like EEM peak intensities, suggesting that these spectroscopic indices could be used to predict TOC oxidation rates. TOC signals from instruments using the UV-sulfate method increased with increasing chamber temperature and increasing UV exposure durations. Signals were more sensitive to the former condition, suggesting that chamber temperature is important for improving the TOC oxidation rates of refractory organic matter.

Optimization of Operation and Backwashing Condition for an Upflow Stormwater Filtration System Utilizing Ceramic Media

Stormwater filtration is widely used for the urban runoff treatment. However, intensive maintenance and lack of information about the performance have resulted in an increased need of proper evaluation. In this study, the performance of an upflow stormwater runoff filtration system, consisting of a supporting unit and a filtration unit filled with a ceramic media, was investigated. The maximum head loss increase was about 3 cm under the suspended solid (SS) load of 30 kg/m 2 and the SS removal was more than 96%, when the filtration velocity was 20-40 m/h. The head loss and the porosity of the media can successfully be described by a power model. It was confirmed that the a significant amount of SS can effectively be removed at supporting unit, minimizing SS load to the filter media bed. Several backwashing strategies have been tested to establish the optimum condition. It was found that the stagnant water discharge is important to minimize the SS release immediately after backwashing. Also, the filter bed loaded with 400-450 kg/m 2 SS can almost completely be washed to reduce the head loss to the that of empty bed. The results in this study indicate that the upflow ceramic media filter is an excellent alternative to stormwater treatment, with high SS removal and long lifespan.

Evaluation of COD sed Analytical Methods for Domestic Freshwater Sediments: Comparison of Reliability and Correlationship between COD Mn and COD Cr Methods

In Korea, the chemical oxygen demand() in freshwater sediments has been measured by the potassium permanganate method used for marine sediment because of the absence of authorized analytical method. However, this method has not been fully verified for the freshwater sediment. Therefore, the use or modification of the potassium permanganate method or the development of the new analytical method may be necessary. In this study, two modified analytical methods such as the modified potassium permanganate method for and the modified closed reflux method using potassium dichromate for were compared. In the preliminary experiment to estimate the capability of the two oxidants for glucose oxidation, and were about 70% and 100% of theoretical oxygen demand(ThOD), respectively, indicating that was very close to the ThOD. The effective titration ranges in and were 3.2 to 7.5 mL and 1.0 to 5.0 mL for glucose, 4.3 to 7.5 mL and 1.4 to 4.3 mL for lake sediment, and 2.5 to 5.8 mL and 3.6 to 4.5 mL for river sediment, respectively, within 10% errors. For estimating recovery(%) in glucose-spiked sediment after aging for 1 day, the mass balances of the and among glucose, sediments and glucose-spiked sediments were compared. The recoveries of and were 78% and 78% in glucose-spiked river sediments, 91% and 86% in glucose-spiked lake sediments, 97% and 104% in glucose-spiked sand, and 134% and 107% in glucose-spiked clay, respectively. In conclusion, both methods have high confidence levels in terms of analytical methodology but show significant different concentrations due to difference in the oxidation powers of the oxidants.