10 research outputs found
ํ ์๋ฏธ์๋ฌผ์ ํ์ฑ์ ์ด์ฉํ ํ์ฝ๋ฅ์ ํ ์ ์ํ๋ ์ฑ ๋ฐ ์ํํ์ ํ์ฉ๋๋ ๊ฒฐ์ ์ ๊ดํ ์ฐ๊ตฌ
ํ์๋
ผ๋ฌธ (์์ฌ)-- ์์ธ๋ํ๊ต ๋ํ์ : ๊ฑด์คํ๊ฒฝ๊ณตํ๋ถ, 2014. 8. ๋จ๊ฒฝํ.์ฌ๊ฒฉ์ฅ ์ค์ผ ํ ์์ ๋ํ ๊ด์ฌ์ด ์ปค์ง๊ณ ์์ผ๋ ์์ง๊น์ง ํ์ฝ๋ฌผ์ง์ ๋ํ ๊ตญ๋ด ๋ฒ๊ท์ ์ ํ๊ธฐ์ค์ด ์กด์ฌํ์ง ์์ ํ์ฝ๋ฌผ์ง์ ์ ํ ๋ฐ ๊ด๋ฆฌํ๊ธฐ์ ๋ง์ ์ด๋ ค์์ ๊ฒช๊ณ ์๋ค. ์ฌ๊ฒฉ์ฅ ๋ด ์ค์ผ๋ฌผ์ง์ ํ์ฝ๋ฌผ์ง ๋ฟ ์๋๋ผ ์ค๊ธ์๋ ๋ฐ๊ฒฌ๋๋, ์ค๊ธ์์ ๊ฒฝ์ฐ ๊ตญ๋ด ๋ฒ๊ท ์ ํ ์ ๊ธฐ์ค์ด ๋๋ถ๋ถ ์กด์ฌํ๋ฉฐ, ์ค๊ธ์์ ์ํ๋
์ฑํ์ ์ํฅ์ ๊ด๋ จํ์ฌ ์ด๋ฏธ ๋ง์ ์ฐ๊ตฌ๊ฐ ์งํ๋์๊ธฐ ๋๋ฌธ์ ๋ณธ ์ฐ๊ตฌ์์๋ ์ฌ๊ฒฉ์ฅ ์ค์ผ ๋ถ์ง์ ์ฃผ์ ์ค์ผ๋ฌผ์ง ์ค์์ ํ์ฝ๋ฌผ์ง์ ์ ์ ํ์๋ค. ํ์ฝ๋ฌผ์ง์ ๋ํ์ ์ผ๋ก 2,4,6-trinitrotoluene (TNT), hexahydroโ1,3,5โtrinitroโ1,3,5-triazine (RDX), 1,3,5,7โtetranitroโ1,3,5,7-tetrazocane (HMX) ์ด๋ ๊ตญ๋ด์์ HMX๋ ์ฌ์ฉํ์ง ์๊ธฐ๋๋ฌธ์ ๊ตญ๋ด ์ค์ ์ ๋ง๋ TNT์ RDX๋ฅผ ๋์ ๋ฌผ์ง๋ก ์ ์ ํ์๋ค.
๋ค์ํ ์ํ์์ฉ์ฒด๋ฅผ ๋์์ผ๋ก ํ ๋
์ฑํ๊ฐ ๊ฒฐ๊ณผ๋ก ๋์ถ๋ ๋
์ฑ์ข
๋ง์ ์ ์ํํ์ ํ ์ ํ์ฉ๋๋๋ฅผ ๋์ถํ๋ ๊ณผ์ ์์ ์ฌ์ฉ๋๋ค. ํ์ง๋ง ๋ฏธ์๋ฌผํ์ฑ์คํ์ ํตํ ํ ์๋ฏธ์๋ฌผ์ ๋ํ ๋
์ฑ์ํฅ์ ํ๊ฐํ ๋
์ฑ ์๋ฃ๊ฐ ๋ถ์กฑํ ์ค์ ์ด๋ค. TNT์ ๊ฒฝ์ฐ ํ ์๋ฏธ์๋ฌผ์ ๋ํ ๋
์ฑ ์ข
๋ง์ ์ด ์กด์ฌํ๋, ๊ทธ์ค ์ผ๋ถ๋ ๋ฏธ์๋ฌผ์ ์์ฒด์ค๋์ ํ๊ฐํ ๊ฒ์ผ๋ก ํ ์๋ฏธ์๋ฌผ ํ์ฑํ๊ฐ๋ฅผ ํตํ ๋
์ฑ์๋ฃ์ ์๊ฐ ๋ถ์กฑํ๋ฉฐ, RDX์ ๊ฒฝ์ฐ ํ ์๋ฏธ์๋ฌผ์ ๋์์ผ๋ก ํ ๋
์ฑ์ํฅ ํ๊ฐ๊ฐ ๊ฑฐ์ ์งํ๋์ง ์์๋ค. ๋ฐ๋ผ์ ๋ณธ ์ฐ๊ตฌ์์๋ ํ ์๋ฏธ์๋ฌผ ํ์ฑํ๊ฐ๋ฅผ ํตํ์ฌ ์ฐจํ ์ํ๋
์ฑํ์ ์ํฅ ํ๊ฐ์ ์ด์ฉ๋ ์ ์๋ ๋
์ฑ์๋ฃ๋ฅผ ์ ์ํ๋ค. ํ ์๋ฏธ์๋ฌผ ํ์ฑํ๊ฐ๋ฅผ ์ํด potential nitrification activity, dehydragenase activity, phosphatase activity, fluorescein diacetate activity, ฮฒ-glucosidase activity, arylsulfatase activity and rhodanese activity, 7๊ฐ์ง์ ํจ์๋ฐ์์ 2์ฃผ, 4์ฃผ ๊ทธ๋ฆฌ๊ณ 8์ฃผ์ ๋
ธ์ถ๊ธฐ๊ฐ์ ๋์ด ์ธก์ ํ์๋ค. ์ด๋ ๋ค์ํ ํ ์ ํน์ฑ์ ๋ฐ๋ฅธ ๋
์ฑ๋ฐํ์ ์ ๋ ๋ณํ๋ฅผ ์์๋ณด๊ธฐ ์ํ์ฌ ์ฌ๊ฒฉ์ฅํ ์, ์์ผํ ์, ๋
ผํ ์, ๋งค๋ฆฝ์งํ ์, ๋ชจ๋, ์ ํ , ์ ๊ธฐ๋ฌผ์ ์ด์ฉํ์ฌ ์คํํ์๋ค. ๊ฐ ํ ์๋ณ, ๊ทธ๋ฆฌ๊ณ ํจ์๋ฐ์๋ณ ์คํ๊ฒฐ๊ณผ์์ NOEC (No Observed Effect Concentration)์ ๋์ถํ ํ ํ๋์ ํจ์๋ฐ์์ ๋ํ ๋ํ์ NOEC ๊ฐ์ ๊ธฐํํ๊ท ์ผ๋ก ๊ณ์ฐํ์๋ค. TNT์ ๊ฒฝ์ฐ, NOEC์ด 45.31 (fluorescein diacetate activity)์์ 55.15 (dehydrogenase activity) mg/kg์ ํด๋นํ๋ ๊ฐ์ ๋ณด์๊ณ RDX์ ๊ฒฝ์ฐ, NOEC ๊ฐ์ด 285.9 (phosphatase activity)์์ 308.9 (dehydrogenase activity) mg/kg์ ํด๋นํ์๋ค.
์ต๊ทผ ๊ตญ์ ์ ์ผ๋ก ์ํ ์์ฉ์ฒด์ ๋ํ ๊ณ ๋ ค๊ฐ ์ ์ฐจ ์ค์ํด์ง๊ณ ์๋ค. ํ ์๋งค์ฒด์ ๊ฒฝ์ฐ ํ ์ ์ํ ์ค์ฌ์ ์ํด์ฑ ํ๊ฐ์ ์ธ์ฒด ์ค์ฌ์ ์ํด์ฑ ํ๊ฐ ๋ชจ๋๋ฅผ ๊ณ ๋ คํ์ฌ ํ ์ ์ค์ผ์ ๊ด๋ฆฌํ๋ ๋ฏธ๊ตญ, ์บ๋๋ค, ๋ค๋ธ๋๋, ๋
์ผ ๋ฑ์ ๊ตญ๊ฐ๋ค๊ณผ ๋ฌ๋ฆฌ ์ฐ๋ฆฌ๋๋ผ์์๋ ์์ง ์ธ์ฒด ์ค์ฌ์ ์ํด์ฑ ํ๊ฐ๋ง ์ด๋ฃจ์ด์ก์ ๋ฟ ์ํ ์์ฉ์ฒด์ ๋ํ ๊ณ ๋ ค๊ฐ ์๋ ์ค์ ์ด๋ค.
๊ตญ๋ด ์์์ข
, ๊ตญ์ ํ์ค ์ํ์ข
, ๊ตญ์ ์์์ข
์ ํฌํจํ์ฌ TNT์ RDX์ ํ ์ ์๋ฌผ์ ๋ํ ๋
์ฑ ์งํ๊ฐ 350์ฌ๊ฐ๋ฅผ ๋ฏธ๊ตญ์ EPA(Environmental Protection Agency), ์บ๋๋ค์ CCME (Canadian Council of Ministers of the Environment) ์ ๋
ผ๋ฌธ์ ํตํด ์กฐ์ฌํ์๊ณ , ์์ง๋ ์๋ฃ๋ qualification ๊ณผ์ ์ ํตํ์ฌ ์ ๋ขฐ๋๊ฐ ๋์ ์๋ฃ๋ง์ ์ ๋ณํ์๋ค. ๋
์ฑ์๋ฃ๋ฅผ ๋์ถํ๋ ๊ณผ์ ์์ ๊ตญ์ ํ์ค ๋
์ฑ์คํ๋ฒ์ ์ฌ์ฉํ์ฌ์ผ ํ๊ณ , ๋
ธ์ถ๊ธฐ๊ฐ, ๋
์ฑ์ข
๋ง์ , ํต๊ณํ์ ์ฒ๋ฆฌ๋ฐฉ๋ฒ, ์ธ๊ณต์ค์ผ ํ ์ค์ ์ค์ผ๋๋ ๊ทธ๋ฆฌ๊ณ ๊ทธ ๋ฐ์ ์คํ ์กฐ๊ฑด์ ๋ํ ์ ํํ ๋ช
์๊ฐ ๋์ด ์์ด์ผ ํ๋ค. ํ ์ ๋
์ฑ ์๋ฃ์ ๊ฒฝ์ฐ ํ ์ ๋ด ์ ๊ธฐ๋ฌผ ํจ๋์ ๋ฐ๋ผ ๋
์ฑ ๋ฐํ์ด ๋ฌ๋ผ์ง ์ ์์ผ๋ฏ๋ก ๊ธฐ์ค ์ ๊ธฐ๋ฌผํจ๋์ ๋ง๋๋ก ํ์คํ ๊ณผ์ ์ ๊ฑฐ์ณค๋ค. ์กฐ๊ฑด์ ๋ง์กฑํ๋ ๋
์ฑ์๋ฃ๋ค์ ๊ธฐํํ๊ท ์ ํตํด ํ๋์ ์ข
๊ณผ ํ๋์ ๋
์ฑ์ข
๋ง์ ์ ๋ํ ๋ํ๊ฐ์ ๊ณ์ฐํ์๋ค. ์์ง๋ ๋
์ฑ์๋ฃ์ quality์ ๋ฐ๋ผ ์ข
๋ฏผ๊ฐ๋๋ถํฌ๋(SSD: Species Sensitivity Distribution), Assessment Factor method (AF), ๊ทธ๋ฆฌ๊ณ Equilibrium Partitioning method ์ค ํ๋์ ๋ฐฉ๋ฒ์ ์ ์ ํ์๋ค.
์ด๋ค ๋ฌผ์ง์ ํ๊ฒฝ๊ธฐ์ค์ ๊ฒฐ์ ํ๋ ๋ฐ์๋ ๊ทธ ๋ฌผ์ง์ ๋
์ฑ๋ฟ ์๋๋ผ ๋ฐฐ๊ฒฝ๋๋, ๊ฐ์ฉํ ์ ํ๊ธฐ์ , ์ฌํ๊ฒฝ์ ์ ๊ณ ๋ ค ๋ฑ์ด ํฌํจ๋์ด์ผ ํ์ง๋ง, ๋ณธ ์ฐ๊ตฌ์์ ๋์ถ๋ TNT์ RDX์ ํ ์ ์๋ฌผ์ด 5% ์ํฅ์ ๋ฐ๋ ๋๋์ธ HC5๋ ์ํ ๋ณดํธ๋ฅผ ์ํ ํ ์์ TNT, RDX ๊ด๋ฆฌ๊ธฐ์ค์ ๊ธฐ๋ณธ ๊ฐ์ผ๋ก๋ ์ฌ์ฉ๋ ์ ์์ ๊ฒ์ด๋ค.
์ฌ๊ฒฉ์ฅ์ ๊ฒฝ์ฐ, ์ฌ๋์ ์ ๊ทผ์ ์ ํ๋์ด ์์ผ๋ ์ฃผ๋ณ ์์ ๋์๋ฌผ์ ์ ๊ทผ์ ๊ฐ๋ฅํ๊ธฐ ๋๋ฌธ์ ํ ์ ์ํ ์์ฉ์ฒด๋ฅผ ๋ฐ๋์ ๊ณ ๋ คํด์ผํ๋ค. ์ค์ ๊ตญ๋ด ๋ค๋ฝ๋ ์ฌ๊ฒฉ์ฅ๊ณผ ์ฃผ๋ณ์ง์ญ์ ์กฐ์ฌํ ๊ฒฐ๊ณผ, ๊ณ ๋ผ๋, ๋ฉง๋ผ์ง, ๋ค๋์ฅ๋ฅผ ํฌํจํ 26 ์ข
์ ํฌ์ ๋ฅ, ์ ๋น, ๊ฑฐ์, ๊น๋ง๊ท๋ฅผ ํฌํจํ 77 ์ข
์ ์กฐ๋ฅ, ๋ถ๋ค, ๊ฐ๋, ๋ฒ๋๋๋ฌด๋ฅผ ํฌํจํ 90 ์ข
์ ์๋ฌผ์ด ๋ฐ๊ฒฌ๋์ด ์ํ ์์ฉ์ฒด ๊ณ ๋ ค์ ํ์์ฑ์ ํ์ธํ์๋ค.
๋ณธ ์ฐ๊ตฌ์์ ๋์ถํ HC5๋ฅผ PNEC (Predicted No Effect Concentration)๋ก ์ฌ์ฉํ๊ณ ํํ๊ฐ ์ ์ญ์ ์๋ ๋ค๋ฝ๋ ์ข
ํฉ์ฌ๊ฒฉ์ฅ TNT, RDX์ ํ ์ ์ค์ผ ๋๋๋ฅผ PEC (Predicted Exposure Concentration)์ผ๋ก ํ์ฌ HQ๏ผHazard Quotient)๋ฅผ ๋์ถํ์ฌ ์ํ ์ํด ์ฌ๋ถ๋ฅผ ํ๋จํ์ฌ ๋ณด์๋ค. ํ ์ ์ค์ผ ๋๋์ธ PEC์ ๋ค๋ฝ๋ ์ข
ํฉ์ฌ๊ฒฉ์ฅ ๋ด ์ค์ํ incermental sampling ๊ฒฐ๊ณผ, ๋ฐ๊ฒฌ๋๋์ ๋ํ๋๋ TNT-40.59 mg/kg (95% Gamma UCL), RDX-52.97 mg/kg (95% chebyshev UCL)์ ์ฌ์ฉํ์๋ค. PNEC์ ๊ฒฝ์ฐ ๋ณธ ์ฐ๊ตฌ์์ ๋์ถํ ๋ค๋ฝ๋ ์ฌ๊ฒฉ์ฅ ์ฃผ๋ณ ํํ๊ฐ์ ์์ํ๊ณ๋ฅผ ๋ณดํธํ ์ ์๋ ์ํํ์ ํ์ฉ๋๋์ธ TNT-807 mg/kg, RDX-56 mg/kg์ ์ฌ์ฉํ์๋ค. ํ ์์์ TNT์ HQ๋ ๋ํ ๋๋์์ 0.05, RDX์ ๊ฒฝ์ฐ 0.95์ด๋ฏ๋ก 1 ์ดํ ๊ฐ์ด ์ฐ์ถ๋์ด ์ํํ์ ์ผ๋ก ์ํด ๊ฐ๋ฅ์ฑ์ด ์๋ ๊ฒ์ผ๋ก ํ๋จ๋์๋ค. ๋์ถํ HQ ๊ฐ์ ๋ค๋ฝ๋ ์ฌ๊ฒฉ์ฅ ํผํ์ง ํ ์์ ์กด์ฌํ๋ TNT์ RDX๊ฐ ์ฃผ๋ณ ์๊ณ์ธ ํํ๊ฐ์ ์๊ณ์ํ๊ณ์ ์ํฅ์ ๋ฏธ์น ๊ฐ๋ฅ์ฑ์ด ์๋ ๊ฒ์ ์๋ฏธํ๋, RDX์ ๊ฒฝ์ฐ 0.95์ด๋ฏ๋ก ์ถ๊ฐ์ ์ธ ํผํ์ง ํ ์์ ๋ํ ์กฐ์ฌ๊ฐ ํ์ํ ๊ฒ์ผ๋ก ํ๋จ๋๋ค.Soil contamination with explosives at firing ranges are recently found to be influential to the surrounding ecosystem. At highly active firing ranges, it is more reasonable to manage the toxic effect of explosives on surrounding ecosystem than the direct remediation of contaminants on site. This study was performed to determine the effects of explosives-contaminated soil and water and to suggest ecologically permissible concentrations of explosives. Among explosives, 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) were selected as target pollutants. Moreover, microbial activity experiments were executed for more qualified derivation of permissible concentrations, since few microbial toxicity data of TNT and RDX were available.
Toxicity data of various species were available, however, the effects of TNT and RDX on microbes were not studied widely, only few soil toxicity data of TNT and RDX on microbes were available. Therefore, the study of toxic effects of TNT and RDX on microbes is required. Soil microbial activity such as potential nitrification activity, dehydragenase activity, phosphatase activity, fluorescein diacetate activity, ฮฒ-glucosidase activity, arylsulfatase activity and rhodanese activity were measured using seven different soil types. NOECs were derived to verify the toxicity of TNT and RDX on soil microbes by calculating the geometric means of NOECs using different soil types each from different enzymatic assay methods. For TNT, NOEC values varied from 45.31 (fluorescein diacetate activity) to 55.15 (dehydrogenase activity) mg/kg and for RDX, NOEC values varied from 285.9 (phosphatase activity) to 308.9 (dehydrogenase activity) mg/kg.
The derivation and suggestion of permissible concentrations of TNT and RDX are required, since there is no standards of TNT and RDX in Korea. The toxicity values of various test organisms from literatures are chosen in order to derive ecological permissible concentrations. The permissible concentrations were derived using guidelines such as A Protocol for the Derivation of Environmental and Human Health Soil Quality Guidelines (CCME) and Guidance for the derivation of environmental risk limits within the framework of International and national environmental quality standards for substances in the Netherlands (RIVM). Ecologically permissible concentrations of TNT and RDX in soil are suggested as TNT-7.7 (UF=5) and 17.3 (UF=1) mg/kg, RDX-18.3 (UC=5) and 41 (UF=1) mg/kg for Dutch RIVM approach and TNT-5.6 (UF=5) and 28.1 (UF=1) mg/kg, RDX-15 (UF=5) and 75 (UF=1) mg/kg for Canadian CCME approach. Each concentrations were derived through selected procedure chosen by quality of each toxicity data sets. The permissible concentrations of TNT varies slightly less than RDX between CCME and RIVM approach. The toxicity data of RDX used for CCME approach might determined to be less qualified because EC50 values were used due to lack of EC20 values. When using this data set, RIVM approach can be determined to be more precise.
For determination of environmental quality standard of each contaminants, not only toxicity but also background concentration, capability and applicability of remediation and management technology and other social/economical conditions should be considered, however ecologically permissible concentrations derived in this study can be used as screening level.
HC5 values which are derived in this study were set to PNEC (Predicted No Effect Concentration), and the measured TNT and RDX concentrations in active firing range soil were set to PEC (Predicted Exposure Concentration). HQ (Hazardous Quotient) was calculated to determine the ecotoxicological risk. PEC were the representative concentration of TNT-40.59 mg/kg (95% Gamma UCL) and RDX-52.97 mg/kg (95% chebyshev UCL) using incremental sampling. Ecologically permissible firing range soil for protecting aquatic species of TNT-807 mg/kg and RDX-56 mg/kg were used for PNEC. The calculated HQ value of TNT was 0.05, and for RDX, it was 0.95 with representative concentrations indicating no ecotoxicological risk are found in this contamination site, however the derived HQ value of RDX was 0.95 which is close to one. It is determined that further investigation on RDX in active firing range is needed.1. Introduction 1
1.1 Background 1
1.2 Objectives 3
1.3 Dissertation Structure 4
2. Literature Review 5
2.1 Ecotoxicity Tests 5
2.1.1 Ecotoxicity Tests on Terrestrial Species 5
2.1.2 Ecotoxicity Tests on Aquatic Species 7
2.2 Ecotoxicity Tests on Soil Microbes 9
2.2.1 Mechanism of Enzyme Action 10
2.2.2 The Activity of Soil Microbes 11
2.2.2.1 Potential nitrification activity 11
2.2.2.2 Dehydrogenase activity 12
2.2.2.3 Phosphatase activity 13
2.2.2.4 Fluorescein diacetate hydrolytic activity 14
2.2.2.5 ฮฒ-glucosidase activity 14
2.2.2.6 Arylsulfatase activity 16
2.2.2.7 Rhodanese activity 17
2.3 Ecotoxicological Risk Assessment 18
2.3.1 Probabilistic Approach 18
2.3.1.1 Species sensitivity distribution 19
2.3.2 Deterministic Approach 21
2.3.2.1 Assessment factor method 21
2.3.2.2 Equilibrium partitioning method 23
2.4 Environmental Quality Standards 25
2.4.1 Setting Soil Quality Standard 25
2.4.1.1 Canadian CCME approach 25
2.4.1.2 Dutch RIVM approach 27
2.4.2 Setting Water Quality Standard 28
3. Materials and Methods 30
3.1 Determination of Microbial Activity in Soil 30
3.1.1 Materials 30
3.1.1.1 Test soil types 30
3.1.1.2 Chemicals and reagents 32
3.1.2 Soil Microbial Activity Test Methods 33
3.1.2.1 Potential nitrification activity 33
3.1.2.2 Dehydrogenase activity 34
3.1.2.3 Phosphatase activity 34
3.1.2.4 Fluorescein diacetate hydrolytic activity 35
3.1.2.5 ฮฒ-glucosidase activity 35
3.1.2.6 Arylsulfatase activity 36
3.1.2.7 Rhodanese activity 36
3.2 Derivation of Ecologically Permissible Concentrations 37
3.2.1 Toxicological Data Qualification Process 37
3.2.1.1 Data collection 37
3.2.1.2 Data screening 39
3.2.1.3 Data qualification 40
3.2.1.4 Data extrapolation type selection 41
3.2.2 Species Sensitivity Distribution (SSD) 41
3.2.2.1 The concept of SSD 41
3.2.2.2 Selection of HC5 43
3.2.3 Derivation of Ecologically Permissible Concentrations 44
3.2.3.1 Ecologically permissible soil concentration 44
3.2.3.2 Ecologically permissible water concentration 44
3.3 Analysis 45
3.3.1 Soil Microbial Activity Analysis 45
3.2.3.1 Ion Chromatography (IC) 45
3.2.3.2 UV/Vis Spectrophotometer 45
3.3.2 Statistics and Data Interpretation 45
3.3.3 TNT and RDX Analysis (HPLC) 46
4. Results and Discussion 47
4.1 Soil Microbial Activity 47
4.1.1 Soil Microbial Activity Test Results 48
4.1.1.1 Potential nitrification activity 49
4.1.1.2 Dehydrogenase activity 50
4.1.1.3 Phosphatase activity 51
4.1.1.4 Fluorescein diacetate hydrolytic activity 52
4.1.1.5 ฮฒ-glucosidase activity 53
4.1.1.6 Arylsulfatase activity 54
4.1.1.7 Rhodanese activity 55
4.1.2 Toxicity Endpoint Suggestion 56
4.2 Derivation of Ecologically Permissible Concentration 57
4.2.1 Ecologically Permissible Soil Concentrations using RIVM Approach 57
4.2.2 Ecologically Permissible Soil Concentrations using CCME Approach 60
4.2.3 Comparison of Ecologically Permissible Soil Concentrations among Major Trophic Levels 63
4.3 Application in Korean Active Firing Range 66
4.3.1 Site Characterization 66
4.3.2 Derivation of Ecologically Permissible Water Concentration 68
4.3.3 Derivation of Ecologically Permissible Active Firing Range Soil Concentration by Efflux Equation 71
4.3.4 Ecotoxicological Risk Assessment at Darakdae Active Firing Range 75
5. Conclusion 77
References 81Maste
์ ๊ธฐ์์ด์จ์ธ tributylmethyl ammonium (TBuMA)์ ์์ฅํก์-์ฉ๋์ฆ๊ฐ๋ฅผ ์ด๊ณผํ๋ ํก์์ฆ๊ฐ ํ์์ ํด์
Thesis(doctoral)--์์ธ๋ํ๊ต ๋ํ์ :์ ์ฝํ๊ณผ ์ฝ์ ๊ณผํ์ ๊ณต,2006.Docto
(A)Study on the degradation and the reduction of acute toxicity of simazine and 4-chloroaniline using photolysis and photocatalysis
Thesis(masters) --์์ธ๋ํ๊ต ๋ํ์ :ํ๊ฒฝ๋ณด๊ฑดํ๊ณผ(ํ๊ฒฝ๋ณด๊ฑดํ์ ๊ณต),2008. 8.Maste
์์ฒด ๋ด ์์์ ์ดํํ์ ๋ฉํธํ ๋ฐ ๋๋ฉํธํ ๋ฐ์์ ๊ธฐ์ ์ฐ๊ตฌ
ํ์๋
ผ๋ฌธ (๋ฐ์ฌ)-- ์์ธ๋ํ๊ต ๋ณด๊ฑด๋ํ์ : ๋ณด๊ฑดํ๊ณผ, 2014. 8. ์กฐ๊ฒฝ๋.Methylmercury (MeHg) is among the most widespread contaminants that pose severe health risks to humans and wildlife. In determination the levels of MeHg in aquatic environments, methylation of inorganic mercury (Hg(II)) to MeHg and demethylation of MeHg are the two most important processes in the cycling of MeHg. So, the knowledge of the efficiency of these different pathways of Hg methylation and demethylation is one of the key steps to predict MeHg concentrations in the different environmental compartments and to estimate the Hg bio-accessibility to the organisms.
However, the factors that influence the competing methylation and demethylation reactions are yet insufficiently understood and little to no attempt has been made to determine end products, especially abiotic processes. The relative importance of each reaction and the resulting net effect will probably depend on the environmental conditions. Therefore, this study investigated the possible photochemical processes and mechanism of Hg demethylation and methylation in water with simulating various environmental conditions. The main objectives of this study were (1) to investigate the influence of several environmental factors and other water constituents on photo-decomposition of MeHg (Study 1), (2) to understand the mechanism of MeHg demethylation process in seawater by assessing the production of dissolved gaseous mercury (DGM) generated from MeHg photo-degradation (Study 2), and (3) to assess the possibility of various methyl donors such as acetate, malonate, dimethylsulfoxide, and litter-derived DOM for photochemical methylation of Hg(II) in aquatic systems (Study 3).
For Study 1, photo-initiated decomposition of MeHg was investigated under UVA irradiation in the presence of natural water constituents including nitrate (NO3โ), ferric (Fe3+), and bicarbonate (HCO3โ) ions, and DOM such as humic and fulvic acid (HA and FA). MeHg degradation followed the pseudo-first-order kineticsthe rate constant increased with increasing UVA intensity ranged from 0.3 to 3.0 mW cm-2. In the presence of NO3โ, Fe3+, and FA, the decomposition rate of MeHg increased significantly due to photosensitization by reactive species such as hydroxyl radical (OHโข). However, the presence of HA and HCO3โ ions lowered the degradation rate through a radical scavenging effect. Increasing the pH of the solution increased the degradation rate constant by enhancing the generation of OHโข. Therefore, OHโข play an important role in the photo-decomposition of MeHg in water, and natural constituents in water can affect the photo-decomposition of MeHg by changing radical production and inhibition.
For Study 2, the photo-induced formation of dissolved gaseous mercury (DGM, Hg0) from MeHg removal was investigated. This study examined the effect of various environmental factors (i.e., light wavelength and intensity and MeHg concentration), and primary water constituents on the abiotic photo-degradation of MeHg, especially under different salinity. Photo-degradation rates of MeHg were positively correlated with the UV light intensity, implying that the attenuation of UV radiation had a significant effect on MeHg photo-degradation in water. However, a high dissolved organic carbon (DOC) concentration and salinity inhibited MeHg photo-degradation. DGM was always produced during the photo-degradation of MeHg. Photo-degradation rates of MeHg and DGM production decreased with increasing salinity, suggesting that the presence of chloride ions inhibited MeHg photo-degradation. Therefore, this study imply that MeHg in freshwater could be more rapidly demethylated than that in seawater and MeHg flowing into the lake or river would be almost removed by photo-demethylation. However, MeHg flowing to seawater would be hardly removed, which could have more chance for bioaccumulation in seawater.
For Study 3, the photochemical methylation of Hg(II) using various methyl donors such as acetate, malonate, dimethylsulfoxide (DMSO), and litter-derived dissolved organic matter (LDOM) was examined. The methylation reaction via acetate was followed the pseudo-first-order kinetics for Hg(II), and the methylation ability of acetate decreased with the solution pH increased. In the Hg(II) methylation by LDOM, LDOM leaded to the production of new MeHg under not only UV irradiation but dark condition. Especially, from the results of the production new MeHg by LDOM in the microbial free and dark condition, this work suggests the possibility that the abiotic chemical reaction such as a non-dependence upon light occurs in the natural aquatic environment. In addition, for the MeHg formation of Hg(II) by DMSO in seawater, abiotic methylation reaction appeared to be promoted via Hg-DMSO complexes, and limited when the reactant is a chloro complex (i.e., seawater) due to its inhibitory effect probably because of higher stability 0of the Hg-Cl bond. Therefore, this study emphasized the importance of possible abiotic methylation by a non-dependence upon light in aquatic systems, while the abiotic chemical reactions for methylation are mostly caused by a dependence upon light up to date.
In conclusion, this thesis achieved MeHg methylation and demethylation through photochemical reaction in aquatic systems. From the results of this thesis, the site-specific environmental factors i.e. environmental conditions of spatial and temporal variations can be effect on the relative importance of each reaction and the resulting net effect in the aquatic environment. In other words, the reduction of MeHg accumulation possibility in aquatic food chain will be mainly affected by the enhancement of demethylation processes with increasing of UV radiation at the surface waters. Ultimately, the results of this thesis could be a significant contribution to understand the possible photochemical processes and mechanism of Hg demethylation and methylation in water and to estimate the factors that influence the competing methylation and demethylation reactions.Contents
Abstract i
List of Tables xii
List of Figures xiv
List of Abbreviations xvi
Chapter 1. Introduction
1.1 Backgrounds 1
1.2 Organomercury Compounds 3
1.3 Mercury methylation and demethylation in aquatic environments 7
1.3.1 Mercury methylation processes 9
1.3.2 Mercury demethylation processes 15
1.4 Objectives 24
Reference 28
Chapter 2. Effect of Natural Water Constituents on the Photo-decomposition of Methylmercury and the role of Hydroxyl Radical
2.1 Introduction 38
2.2 Materials and Methods 42
2.2.1 Reagents and sample preparation 42
2.2.2 Photo-reactor and experimental design 43
2.2.3 Analytical methods 46
2.3 Results and Discussion 48
2.3.1 Effect of UV light intensity 48
2.3.2 Effect of pH 52
2.3.3 Effect of Fe3+ ions 55
2.3.4 Effect of NO3- ions 58
2.3.5 Effect of HCO3- ions 62
2.3.6 Effect of DOM 65
2.4 Conclusions 71
References 72
Chapter 3. The Production of Dissolved Gaseous Mercury from MeHg Photo-degradation at Different Salinity
3.1 Introduction 77
3.2 Materials and Methods 80
3.2.1 Sampling and materials 80
3.2.2 Photo-reactor and experimental design 80
3.2.3 Analytical methods 83
3.3 Results and Discussion 85
3.3.1 Effect of UV light wavelength and intensity on MeHg degradation 85
3.3.2 Effect of salinity on MeHg degradation 90
3.3.3 DGM production during MeHg photo-degradation 93
3.3.4 Effect of salinity on DGM production in the presence of nitrate and bicarbonate ions 96
3.3.5 Effect of DOM 101
3.4 Conclusions 104
References 105
Chapter 4. Photochemical Methylation of Inorganic Mercury by Various Organic Compounds
4.1 Introduction 110
4.2 Materials and Methods 114
4.2.1 Materials 114
4.2.2 Photochemical experiments 114
4.2.3 Molecular weight fractionation of DOM experiment 115
4.2.4 Analysis of mercury and other environmental parameters 116
4.3 Results and Discussion 119
4.3.1 Effect of UV irradiation and incubation time 119
4.3.2 Effect of different LMWOMs 123
4.3.3 Effect of pH 125
4.3.4 Effect of DOM derived from litter 128
4.3.5 Effect of DOM-fractions on methylation 132
4.3.6 Reactions between Hg(II) and DMSO in seawater 137
4.4 Conclusion 140
References 142
Chapter 5. Conclusions
5.1 Conclusions 146
5.2 Implications 148
๊ตญ๋ฌธ์ด๋ก 151
List of Tables
Table 2.1. Photo-decomposition rate constants (RdeMeHg) and half-lives (t1/2) as a function of UVA intensities 51
Table 2.2. Effect of Fe3+ ion concentration on the photo-decomposition rate (RdeMeHg) of MeHg 57
Table 2.3. Effect of NO3- ion concentration on the photo-decomposition rate (RdeMeHg) of MeHg 61
Table 2.4. Effect of HCO3- ion concentration on the photo-degradation of MeHg in the presence of 50 ฮผM Fe3+ ion 64
Table 2.5. Effect of fulvic and humic acid concentrations (mg C L-1) on the photo-decomposition rate (RdeMeHg) of MeHg 67
Table 2.6. Effect of humic acid on the photo-decomposition rate (RdeMeHg) of MeHg in the presence of NO3- ion 70
Table 3.1. The effect of salinity on the rate of MeHg photo-degradation 92
Table 3.2. The effect of salinity on DGM production from MeHg photo-degradation under UVA 98
Table 3.3. The effect of salinity on the rate of MeHg photo-degradation in the presence of nitrate or bicarbonate ions under UVA 99
Table 3.4. The effect of salinity on DGM production in the presence of nitrate or bicarbonate ion under UVA 100
Table 3.5. The effect of DOC concentration on the rate of MeHg photo-degradation and DGM production under UVA 103
Table 4.1. Concentration of MeHg and THg the present of LDOM with and without UVA irradiation 131
Table 4.2. Total organic carbon concentration of the resulting fractions after dialysis 136
Table 4.3. The effect of DOM-fractions on methylation of Hg(II) with UVA irradiation 136
List of Figures
Fig. 1.1. Cycling of mercury in aquatic environment 6
Fig. 1.2. Proposed pathway for methylation of mercury in Desulfovibrio desulfuricans 13
Fig. 1.3. Schematic diagram of the overall composition in the dissertation 27
Fig. 2.1. Schematic diagram of experimental design for photo-decomposition of MeHg 45
Fig. 2.2. Effect of UVA intensity on the photo-decomposition of MeHg 49
Fig. 2.3. Effect of pH on the photo-decomposition rate of MeHg 54
Fig. 2.4. Effect of NO3- concentration on the photo-decomposition rate of MeHg 60
Fig. 2.5. Comparison of absorbance spectrum of humic acid and MeHg 68
Fig. 3.1. A schematic diagram of the experimental design used to investigate the photochemical decomposition of MeHg 82
Fig. 3.2. Photo-degradation kinetics of MeHg under UVA and (b) UVB 86
Fig. 3.3. Photo-degradation rate constants as a function of different UV intensities 88
Fig. 3.4. The effect of the MeHg concentration on the rate of photo-degradation under UVA and UVB 89
Fig. 3.5. Dissolved gaseous mercury production from MeHg photo-degradation under UVA and UVB 95
Fig. 4.1. Effect of UV irradiation on the methylation of Hg in the presence of acetate 121
Fig. 4.2. First-order rate plots at different UV irradiation 122
Fig. 4.3. Effect of concentration of methyl donors under UV irradiation on the methylation of Hg 124
Fig. 4.4. Effect of pH on the methylation of Hg in the present of acetate 127
Fig. 4.5. Comparison of fluorescence spectrum of LDOM size-fractionation into three molecular size group 135
Fig. 4.6. MeHg formation of Hg(II) via DMSO in different salinity 139
Fig. 5.1. Possible pathways of MeHg photo-demethylation to enhance and to inhibit in aquatic environments 150
List of Abbreviations
CVAFS Cold Vapor Atomic Fluorescence Spectrometer
CH3โข Methyl radical
DGM Dissolved Gaseous Mercury
DMS Dimethylsulfide
DMSO Dimethylsulfoxide
DOC Dissolved Organic Carbon
DOM Dissolved Organic Matter
EtHg Ethylmercury
FA Fulvic acid
Fe(OH)2+ Ferrous hydroxide ion
Fe3+ Ferric ion
HA Humic acid
HCO3โ Bicarbonate ion
Hg Mercury
Hg(0) Elemental mercury
Hg(II) Divalent mercury
Hg22+ Dimeric mercury ion
HMWOC High-molecular-weight Organic Compound
LMWOC Low-molecular-weight Organic Compound
LOI Loss On Ignition
MeHg Methylmercury
NO2โ Nitrile ion
NO3โ Nitrate ion
NOM Natural Organic Matter
1O2 Singlet oxygen
OC Organic Carbon
OHโข Hydroxyl radical
OM Organic Matter
OOCH3โข Peroxomethyl radical
r2 Determination coefficient
RO2โข Organic peroxy radical
ROS Reactive Oxygen Species
SRB Sulfate-reducing Bacteria
SRHA Standard Suwanee River humic acid
SRFA Standard Suwanee River Fulvic Acid
SRM Standard Reference Matter
THg Total mercury
US EPA United States Environmental Protection Agency
UV Ultra VioletDocto