형광 3D-EEMs를 이용한 시화호유역 하천 및 공단폐수의 유기물 특성 분석

이미경(Mi Kyung Lee),최광순(Kwang Soon Choi),김세원(Sea Won Kim),김동섭(Dong Sup Kim) 大韓環境工學會 2009 대한환경공학회지 Vol.31 No.9

본 연구에서는 유역특성이 뚜렷이 구분되는 시화호 유역(농촌, 도심지역, 공단지역)의 하천수 및 공단폐수를 대상으로 형광 3D-EEMs (3-Dimensional Excitation Emission Matrix Spectroscopy)를 이용하여 DOM (Dissolved Organic Matter)의 공간적 분포 특성을 파악하였다. 또한, 강우시 synchronous와 3D-EEMs를 이용하여 시간에 따른 DOM의 변화 특성을 보았다. 3D-EEMs로 부터 나타난 주요 DOM 물질은 휴믹계물질(Humic Like Substances, HLS)과 단백질계물질(Protein Like Substances, PLS)로 농촌 및 도심유역에서는 HLS가 주로 분포하였으며, 공단유역에서는 HLS 뿐만 아니라, PLS도 높게 나타났다. 각 지점별 DOM의 형광 peak T1:C1 ratio로 부터 반월공단(3TG)에서 난분 해성 휴믹계 물질이 매우 높은 것으로 나타났다. 또한, 조사지점의 PLS 물질(peak T1, peak B1)과 BOD 농도가 직선의 상관성(r2=0.65, r2=0.66)을 보여, 이러한 원인은 하수 유입 등에 의한 영향으로 보인다. 강우시(Rainfall, 30 mm) 시간에 따른 DOM의 모니터링 결과, 농촌유역에서는 HLS와 PLS가 비강우시와 비교하여 형광세기만 높아졌을 뿐, 구성 물질의 변화 특성은 보이지 않았다. 한편, 도심유역에서는 HLS의 강우 초기 30분 내에 유출이 높은 것으로 나타났으며, 공단 유역(4TG)에서도 강우 초기 20분 내에 HLS와 PLS의 유출이 매우 높게 나타났다. 본 연구로부터 형광 3D-EEMs는 유역의 DOM 기원을 밝히고, 비점오염원 및 하·폐수를 모니터링 하는데 있어 유용한 tool로 적용될 수 있음을 제시한다. This study is conducted to examine spatial variations of Dissolved Organic Matter (DOM) in stream and waste waters of the different watershed areas (agricultural, residential, and industrial complex area) by using fluorescence 3D-EEMs (3 Dimensional Excitation Emission Matrix Spectroscopy). Furthermore, the research investigates the changes of DOM characterization by synchronous and 3D-EEMs during a rainfall event. The characterizations of DOM obtained by 3D-EEMs show two noticeable peaks at humic and protein-like regions. Humic-like substances (HLS) are found in rural and urban areas, and humic and protein-like substances (PLS) are shown in industrial area. According to the fluorescence peak T1:C1 ratios, it is observed that high amount of HLS was discharged from Banweol Industrial Complex (3TG). Additionally, linear relationships (Regression rate, r2=0.65, r2=0.66) have been shown between PLS (peak T1, B1) and biochemical oxygen demand (BOD), which indicates the impact of sewage. For the rainfall event (30 mm), no remarkable difference of DOM was found at rural area except increment of fluorescence intensity comparing dry period. In contrast, HLS at urban area is highly discharged within 30 minutes from the beginning of rainfall. Also, there are high influences of HLS and PLS within 20 minutes at industrial complex (4TG). Fluorescence 3D-EEMs has not only verifies a watershed of DOM origination but also monitors diffuse and point source impacts.

Chemical Structural Features of Humic-like Substances (HULIS) in Urban Atmospheric Aerosols Collected from Central Tokyo with Special Reference to Nuclear Magnetic Resonance Spectra

Naoya Katsumi,Shuhei Miyake,Hiroshi Okochi 한국대기환경학회 2018 Asian Journal of Atmospheric Environment (AJAE) Vol.12 No.2

We measured 1H and 13C nuclear magnetic resonance (NMR) spectra of Humic-like substances (HULIS) in urban atmospheric aerosols isolated by diethylaminoethyl (DEAE) and hydrophilic-lipophilic balance (HLB) resin to characterize their chemical structure. HULIS isolated by DEAE resin were characterized by relatively high contents of aromatic protons and relatively low contents of aliphatic protons in comparison with HULIS isolated by HLB resin, while the contents of protons bound to oxygenated aliphatic carbon atoms were similar. These results were consistent with the results of the 13C NMR analysis and indicate that hydrophobic components were more selectively adsorbed onto HLB, while DEAE resins selectively retained aromatic carboxylic acids. Furthermore, we demonstrated that the chemical structural features of HULIS were significantly different between spring and summer samples and that these disparities were reflective of their different sources. The estimated concentrations of HULIS in spring were found to be regulated by vehicle emissions and pollen dispersion, while the behavior of HULIS in summer was similar to photochemical oxidant and nitrogen dioxide concentrations. The proportion of aliphatic protons for summer samples was higher than that for spring samples, while the proportion of aromatic protons for summer samples was lower than that for spring samples. These seasonal changes of the chemical structure may also involve in their functional expression in the atmosphere.

Characterization, sources, and light absorption of fine organic aerosols during summer and winter at an urban site

Park, Seungshik,Son, Se-Chang,Lee, Sangil Elsevier 2018 Atmospheric research Vol.213 No.-

<P><B>Abstract</B></P> <P>In this study, the 24-h PM<SUB>2.5</SUB> samples were collected from an urban site in Korea during summer and winter. The collected samples were analyzed for organic carbon (OC), elemental carbon (EC), water-soluble OC, humic-like substances (HULIS), and ionic species. Furthermore, in-situ measurements of PM<SUB>2.5</SUB> aerosol absorption coefficients were made by using a dual-spot multi-wavelength Aethalometer. Primary traffic emissions and secondary formation were the major contributors to the HULIS concentration during summer. Furthermore, biomass burning (BB) contributed to HULIS concentration to a certain extent. During winter, the HULIS with higher OC/EC ratio (6.4) were strongly associated with BB and secondary formation, while the HULIS with lower OC/EC ratio (2.9) was mainly attributed to secondary formation and, to a certain extent, primary combustion sources. Light absorption by brown carbon (BrC) was significantly enhanced in the near-ultraviolet and visible spectral regions and exhibited strong spectral dependence. Ambient BrC absorption was estimated to account for 2.1–16.6% and 5.9–29.3% of the total aerosol absorption during summer and winter, respectively. The average values of absorption Ångström exponent (AAE) in the wavelength range of 370–660 nm for light-absorbing BrC aerosols were estimated to be 4.0 and 4.4 during summer and winter, respectively. This study demonstrates that the AAE values for BrC can be derived from multi-wavelength Aethalometer data without filter sampling and detailed laboratory analysis.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Water-soluble HULIS and aerosol light absorption were measured. </LI> <LI> Formation processes of HULIS were discussed. </LI> <LI> Contributions of BC and BrC from aerosol light absorption were estimated. </LI> <LI> Absorption Ångström exponent of BrC was derived without detailed laboratory analysis. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Relationship between carbonaceous components and aerosol light absorption during winter at an urban site of Gwangju, Korea

Park, Seung Shik,Son, Se-Chang Elsevier 2017 Atmospheric research Vol.185 No.-

<P><B>Abstract</B></P> <P>To examine the relationship between the chemical composition of light-absorbing organic aerosols and the absorption properties of the aerosols, daily PM<SUB>2.5</SUB> samples were collected during winter at an urban site of Gwangju, Korea, and analyzed for organic carbon and elemental carbon (OC and EC), water-soluble organic carbon (WSOC), humic-like substances (HULIS), and water-soluble inorganic substances. The real-time black carbon (BC) concentration in PM<SUB>2.5</SUB> was also measured using a dual-spot aethalometer. During the study period, average WSOC/OC and HULIS-C/WSOC ratios were 0.53 and 0.52, respectively. K<SUP>+</SUP>/EC and K<SUP>+</SUP>/OC ratios indicate that biomass burning (BB) emissions are a possible source of the observed carbonaceous aerosols and K<SUP>+</SUP>. Moderate-to-strong correlations of HULIS with NO<SUB>3</SUB> <SUP>−</SUP>, oxalate, SO<SUB>4</SUB> <SUP>2−</SUP>, K<SUP>+</SUP>, CO, and ΔBC (=BC<SUB>@370nm</SUB> −BC<SUB>@880nm</SUB>) suggest that in addition to the primary BB emissions, secondary processing is another important contributor to the formation of HULIS in winter at the site.</P> <P>The average absorption Ångstrӧm exponent (α) of fine aerosols for the wavelengths of 370–950nm and 590–950nm was 1.29 and 1.18, respectively, but the aerosol α value was higher in the near UV wavelength range (370–520nm), with an average of 1.51 (0.76–2.36), indicating that aerosol absorption characteristics during winter were influenced by BB aerosol sources, as well as by traffic emissions. Over the study period, the α<SUB>370–520nm</SUB> value during the highest EC, highest OC, and Asian dust events was 1.42±0.10 (1.26–1.59), 1.44±0.15 (1.16–1.68), and 1.90±0.28 (1.54–2.36), respectively. Higher α<SUB>370–520nm</SUB> values during the Asian dust event were attributed to the influence of dust particles. In addition, the light absorption coefficients of aerosols at 370nm were strongly correlated with OC (R<SUP>2</SUP> =0.76), water-insoluble OC (R<SUP>2</SUP> =0.70), and water-soluble HULIS (R<SUP>2</SUP> =0.64). These tight correlations suggest that water-insoluble fractions of OC, as well as the water-soluble brown carbon, could be important contributors to aerosol light absorption. This study demonstrates that a newly-developed dual-spot aethalometer could be utilized to characterize light absorption properties of organic aerosols and dust particles.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Sources and formation processes of water-soluble HULIS in wintertime were examined. </LI> <LI> A dual-spot aethalometer was used to characterize the aerosol absorption properties. </LI> <LI> Spectral characteristics of aerosol light absorption were discussed. </LI> <LI> Water-insoluble OC and HULIS contributed significantly to aerosol light absorption. </LI> </UL> </P>

영산강 수계 자연유기물질의 계절별 형광특성 연구

조재원 ( Jae Weon Cho ) 한국하천호수학회 2012 생태와 환경 Vol.45 No.1

This study investigated the characteristics of natural organic matter (NOM) with general water characteristics (pH, DO, electrical conductivity, BOD, COD, TN, TP, Chl-a, DOC, UV254, SUVA) and the 3D fluorescence excitation-emission matrix (FEEM) in the Yeongsan River basin. FEEM was used to classify protein-like and fulvic & humiclike substances with fluorescence intensity in the matrix of excitation and emission wavelength. The concentration of BOD, COD, TN, electrical conductivity and DOC in the region of Gwangju city (Gwangju sewage treatment plant: GJS, Gwangjucheon: GJC, Gwangju 2: GJ2) was relatively higher than the upper reaches and lower reaches of the Yeongsan River basin. SUVA in most sites was lower than 3 L mg--1 m--1 as the hydrophilic substances, except Damyang (DY) in the upper reaches of Yeongsan river was higher than 3 L mg--1 m--1 as the hydrophobic substances during winter and autumn. In the FEEM investigation the fulvic and humic substances were found in most sites, and in sites regarding Gwangju city (GJS, GJC, GJ2) during winter and GJC in summer, protein-like substances were found. The trend of fluorescence intensities from the upper reaches to the lower reaches in most sites corresponded to that regarding the concentration of water characteristics (BOD, COD, TN, DOC). That is why the region of Gwangju city (GJS, GJC, GJ2) was relatively higher. This results were an equivalent trend to those of fluorescence index (FI) in most sites, and the higher FIs in the sites of Gwangju city indicate more microbial-derived substances due to enormous effluent organic matters (EfOM) from huge Gwangju sewage treatment plants.

The Possibility of Anabaena Flos-Aquae Spontaneously Form Humus

Yan Li,Sen Dou,Xiangling Tian 한국토양비료학회 2014 한국토양비료학회 학술발표회 초록집 Vol.2014 No.6