수은 및 수은화합물의 배출로부터 국민의 건강 및 환경을 보호하기 위하여 국제수은협약(Minamata Convention on Mercury)이 채택되었다. 수은은 체내 비교적 미량이 노출되어도 생물체에 강한 독성을 나타낸다. 또한 수은으로 오염된 폐기물을 처리 및 처분하는 과정에서 수은이 환경으로 유출될 가능성이 존재하여 배출 규제 강화 및 관리에 관심이 집중되고 있다. 공정에서 배출되는 액상 수은 폐기물에는 용해된 수은 및 수은화합물과 고형물 형태의 것이 함유되어 있다. 따라서 폐기물의 특성에 적합한 수은의 제어가 필요하다. 본 연구에서는 국내 산업시설에서 공정부산물로 발생하는 액상 수은 폐기물을 처리하기 위하여, 총 ６단으로 구성된 흡착설비를 구축하였다. 1~2단계는 각각 10㎛, 5㎛입경의 섬유 필터(MICRO Filter)를 사용하였다. HgCl2는 타 수은화합물에 비하여 수용성이 크고 폐수에 잔류할 가능성이 높다. 따라서 3~5단계는 Cl2제거 효과가 있는 활성탄 필터(CTO Filter)를 사용하였다. 액상 수은 폐기물의 처리 용량을 평가하기 위해 시료의 투입 유량 60 L/hr, 90 L/hr 및 150 L/hr로 달리하여 실험을 진행하였다. MICRO 필터 및 활성탄 필터(CTO Filter)의 수은 제거 효율은 최종단계에서 각 유량별로 96%, 92%, 86%으로 확인되었다. 액상 폐기물 시료에서 수은 화합물을 제거하는데 사용된 필터의 수은 함유 농도를 분석한 결과, 30.3~61.8 mg-Hg/kg으로 분석되었다. 액상 폐기물 수은 제거를 위하여 사용된 필터는 수은 오염 폐기물로써 적정 처리가 필요하다. 시료에 함유된 수은 화합물의 특성에 적합한 필터의 개발 및 사용된 필터의 적정 처리 방법에 대한 연구가 필요하다.

This study investigates leaching and thermal treatment characteristics of mercury in waste phosphor powder from UV lamp for industrial use. Waste phosphor powder contaminated with mercury compounds requires proper treatment for final disposal. A sequential extraction procedure was conducted in order to estimate the stability of mercury compounds in waste phosphor powder. The fraction of mercury compounds leached in initial steps by ion-exchangeable and low acidic solutions was 62%, which would be unstable. Finally 36% of mercury compounds was left as a strongly stable form before last step of acid digestion by aqua regia. Mercury was decomposed rapidly during initial period in thermal treatment. However, the decomposition rate reached in steady later. Correlation of mercury content in residues with concentration of leaching extract was attempted in order to set a thermal treatment condition. When mercury content in residue of phosphor powder could be lowed up to about 13 mg-Hg/kg by thermally with satisfying the Korean leaching standard limit of 0.005 mg-Hg/L.

The re-emission of mercury (Hg), as a consequence of the formation and dissociation of the unstable complex HgSO3, is a problem encountered in flue gas desulphurization (FGD) treatment in coal-fired power plants. A model following a pseudo-second-order rate law for Hg2+ reduction was derived as a function of [SO32-], [H+] and temperature and fitted with experimentally obtained data to generate kinetic rate values of (0.120 ± 0.04, 0.847 ± 0.07, 1.35 ± 0.4) mM-1 for 40°, 60°, and 75℃, respectively. The reduction of Hg2+ increases with a temperature increase but shows an inverse relationship with proton concentration. Plotting the model-fitted kinetic rate constants yields ΔH = 61.7 ± 1.82 kJ mol-1, which is in good agreement with literature values for the formation of Hg0 by SO32-. The model could be used to better understand the overall Hg2+ re-emission by SO32- happening in aquatic systems such as FGD wastewaters.

Elemental mercury has a very high volatility allowing easy dissipation from water or soil into air. To better understand how the kinetics of diffusion of elemental mercury through a medium, which is soil in this study, a mercury diffusion column experiment was done. The correlation between temperature and equilibrium concentrations of mercury in standardized soil samples and a pure mercury standard were determined. Total mercury concentrations were analysed using CVAFS. The effect of time and soil depth to the kinetics of mercury diffusion were determined. Differences in mercury concentrations at different sampling probes were observed during the first few gas phase analyses. Equilibrium was reached through the column after 72 hours.

수은은 온도계, 혈압계, 치과용 아말감, 전지, 형광등과 의약품 등 많이 사용되고 산업적으로도 전기 스위치, 촉매 등으로 중요하게 사용된다. 수은은 증기 흡입 시 폐렴을 유발하고 중추신경계와 신장에 영향을 줄 수 있을 정도로 매우 위험하여 수은과 수은 화합물의 사용이 금지되거나 제한을 받고 있으며, 대체물질과 대체 공정의 개발을 위한 노력이 행해지고 있다. 최근 연이은 병원, 학교 등의 혈압계, 온도계의 수은 누출사고와 형광등 생산시설인 (주)남영전구 광주공장의 해체 및 철거 중 수은 누출로 인한 근로자의 수은 중독 및 환경오염 사고와 비철금속업체의 수은 폐기물 처리문제가 대두되었다. 전국 병원 2,500개소 설문조사 결과, 143개 병원에서 혈압 및 체온계의 약 4천여개(수은량 : 약 140 kg)가 회수와 폐기가 필요한 것으로 조사되었다. 또한 미나마타 협약에서 요구되는 수은 수출･입, 공급원 파악, 임시보관 및 유통･보관, 회수, 처리 등 단계별 수은의 회수, 유통, 관리에 대한 체계 구축이 미흡하다. 수은폐기물은 미나마타협약에 의하여 ‘수은 구성 폐기물’, ‘수은 함유 폐기물’, ‘수은 오염 폐기물’로 나눠지고 본 연구에서는 ‘수은 함유 폐기물과 오염 폐기물’의 수입, 유통, 회수, 폐기 등 전과정 단계별 흐름 분석을 통하여 수은의 국내 흐름을 파악하고 관련 법 제도의 문제점을 분석하고자 함에 있다. 또한 수은 관련 유통량을 조사하고 폐기물의 처리 공정을 파악하여 대상 물질, 원료 사용량, 시스템 경계 설정, 데이터 수집 및 분석, 계산과 검증 등의 절차를 걸쳐 물질수지에 근거하여 ‘물질흐름도’를 작성하여 도출하였다. 물질흐름분석을 보다 쉽게 활용하고 적용할 수 있도록 ‘물질흐름분석 소프트웨어(STAN 2.5)를 활용하여 공정 내의 데이터 유입과 유출을 Shankey diagram 형태로 표현하였다. 연구 결과, 원자재 수은의 국내 유통량은 2014년 기준 국내 유입량은 약 3톤(제조량: 1 ton, 수입량: 2 ton)으로 집계되고 수입된 수은은 대부분 형광램프 제조(2.01 ton), 시약(0.76 ton), 촉매(0.12 ton) 등의 용도로 사용된 것으로 나타났다. 회수량은 문헌 조사 결과 수은 함유 부산물 및 폐기물 관리를 위해 도입되는 시나리오별 두 가지 기준을 적용하여 회수 가능량을 추정하였다. 시나리오에 따라 27.3 ton/yr, 25.4 ton/yr으로 예측하였다. 원자재 수은의 국내 재고량은 대략 0.5 ton/yr으로 보인다.

This study focused on the evaluation of stability of mercury compounds in byproducts from industrial facilities. Stability testing was conducted using a 5-step sequential extraction procedure using six kinds of byproducts. The mercury compounds extracted were categorized as ion-exchangeable (F1), acid soluble (F2), organic matter-bound (F3), strong complex (F4), and residual (F5) mercury compounds. The amount of mercury in each step was calculated and compared with total mercury amount; a 51% to 92% recovery rate was estimated. Hg-extracted F1, F2, and F3 were easily released into environment. It is necessary to apply an appropriate method to handle byproducts that contain these portions of mercury. On the other hand, mercury in F4 and F5 fraction is relatively more stable. F4 fraction means strong complex and elemental mercury. Byproduct from metal production facility has a higher elemental mercury fraction. It was found that 89% and 65% of mercury were contained in F4 fractions from fly ash and sludge, respectively. The goal of this study is to investigate stability of Hg compounds in different byproducts to suggest appropriate treatment methods for each byproduct on its Hg compound characteristics.

This study provides an experimental result of thermal mercury reduction and condensation characteristics for inventing a mercury recovery technology from the waste sludge which contains high concentration of mercury. Thermal treatment was conducted in the temperature range of up to 900oC from 600oC with different residence time using a waste sludge from domestic industrial facility. Properties of powder material condensed after thermal treatment were analyzed to assess the effectiveness of thermal processing. Leaching characteristics of bottom ash and condensed powder material were analyzed by Korean Standard Leaching Test method (KSLT). Cold vapor atomic absorption spectroscopy (CVAAS) Hg analyzer was used for the analysis of mercury content in solid and liquid samples. We found that mercury contents was concentrated compared with waste sludge. However, the mercury concentration of leached solution from the condensed powder material was very low. The chemical characteristics of condensed powder material was estimated using experimental analysis and literature survey. In order to recover purified elemental mercury, the further researches of refining experiments would be required.

본 연구는 돌연변이원(mutagen)의 하나인 메틸수은(methylmercuric chloride, MMC)의 세포독성을 알아보기 위하여 배양 NIH3T3 섬유모세포를 재료로 메틸수은의 독성을 산화적 손상측 면에서 조사하였으며, 또한 메틸수은의 세포독성에 대한 꿀풀 (Prunella vulgaris L. var lilacina Nakai) 추출물의 영향을 세포 생존율을 비롯한 SOD-유사 활성(SOD-like activity) 및 지질과산 화(lipid peroxidation, LP) 저해능과 같은 항산화 측면에서 분석 하였다. 본 실험에서 배양 NIH3T3 섬유모세포에 15∼35uM의 메 틸수은을 처리한 결과 처리농도에 비례하여 세포생존율이 대조군 에 비하여 유의하게 감소하였으며, 또한 XTT50값이 34.2uM에서 나타나 고독성(highly-toxic)인 것으로 나타났다. 한편, 항산화제 인 vitamin E는 메틸수은에 의하여 감소된 세포생존율을 유의하게 증가시켰다. 메틸수은의 세포독성에 대한 꿀풀 추출물의 영향에 있 어서, 꿀풀 추출물은 메틸수은에 의하여 감소된 세포생존율을 유의 하게 증가시킴으로서 메틸수은의 세포독성을 방어하였으며, 동시 에, SOD-유사 활성 및 지질과산화 저해능을 보임으로서 항산화능 을 나타냈다. 위의 결과로 부터 메틸수은의 세포독성에 산화적 손 상이 관여하고 있으며, 동시에 꿀풀 추출물은 항산화능에 의하여 메틸수은의 산화적 손상을 효과적으로 방어하였다. 따라서, 꿀풀 추출물과 같은 천연물질은 메틸수은과 같이 산화적 손상과 관련된 중금속의 독성을 방어 내지는 치료하는데 있어 항산화 소재로서의 유효한 기능이 있음을 제시하고 있다.

In a mercury leaching test for waste using the Korean Standard Method (ES 06404.1), the pre-treatment process of an eluate is very complicated with a high possibility of contamination and low mercury recovery rate. It is also difficult to analyze multiple samples in a short time and the process generates experimental wastes. Accordingly, a direct mercury analyzer (DMA) applying thermal decomposition gold-amalgamation analysis has been recently used. The method shows a relatively high recovery rate for solid samples without complicated pre-treatment and it can be applied to both liquid and solid samples as the EPA method 7473 does. In order to use the auto-sampler in DMA for analyzing many elution samples from waste, this study checked recovery rates depending on acid solutions and additives during continuous analysis. The result showed a significant drop in recovery and precision except for an L-cysteine added sample. Considering commonly used acid-treatment of wastes, three types of acid solutions (nitrate, hydrochloric acid and sulfate) were chosen for analysis, and precision and accuracy were relatively high in nitric acid solution. It has been determined that accuracy and precision improved when 0.01% L-cysteine was added as an additive and this reduced the impact of continuous measurement. Therefore, during analysis of liquid samples or eluted samples using DMA continuously, introducing suitable additives is necessary depending on pre-treatment method in order to improve accuracy and precision in the analysis of mercury.

Mercury distribution and hazardous characteristics of major components from SCFLs (Spent compact fluorescent lamps)for 3 lamp manufactures (A, B, C) are estimated by the analysis of mercury concentration and leaching tests such asKorean Extraction Test (KET) and Toxicity Characteristic Leaching Procedure (TCLP). SCFLs can be separated into glasstube, phosphor powder, metals, ballast, plastics, and binder. Through the analysis of mercury in major components forSCFL, mercury concentration in phosphor powder is much higher than that in other components regardless manufacturesof lamp. Also, mercury concentration in phosphor powder is dependent of the manufactures of lamp. From the leachingtests, all components except phosphor powder from 3 lamp manufactures are verified to be non-hazardous waste becauseall leaching concentrations are below the regulatory level. However, the leaching concentration of mercury in phosphorpowder of SCFLs is higher than the regulatory level in both KET and TCLP regardless manufactures of lamp. Hence,phosphor powder should be managed as a hazardous waste and should be separately managed to control mercury.

This study provides a result of thermal mercury reduction for inventing a mercury recovery technology from the sludgewhich contains high concentration of mercury. Physical, chemical and thermal properties of the sludge were analyzed andmercury degradation at elevated temperatures was investigated to find out the optimum temperature range for thermalrecovery of mercury from the sludge generated from an industrial facility, which contained high concentration of mercury.The study was carried out in the temperature range of up to 650oC from 200oC, and 500~710µm particle size of wastesludge samples were selected from such industries. As primary thermal tests the sludge was heated up to observe weightdegradation at a continuous weight measurable thermogravimetric analyzer and a muffle furnace and the degradationcurves from both devices were found to be well matched. Mercury conversion to gaseous form was investigated fromthe analyzed data of mercury concentrations sampled every 25oC from a muffle furnace. Cold vapor atomic absorptionspectroscopy (CVAAS) Hg analyzer was used for the analysis of mercury content in solid and liquid samples. Most ofmercury was degraded and released as gas phase at the temperature range from 300oC to 550oC, which could be theoptimum temperature of mercury recovery by thermal method for the sludge containing high concentration of mercury.Based on these thermal mercury reduction studies, degradation kinetics study of mercury was conducted to provide thereaction kinetics data for further reactor design to recover mercury using a thermal method.

Ocean dumping of sewage sludge has been prohibited since 2012. Therefore, various methods to recycle sewage sludgeare studied And the adsorption is used to remove mercury released to the atmosphere. Chlorine and Iodine impregnatedadsorbent is used to remove mercury in the flue gas. In our study, we studied the method to recycle sewage sludge andbrewers grain as an adsorbent to remove mercury. Thermal treating time and temperature, and mixing ratio of sewage sludgeand brewers grain are discussed for the preparation of adsorbent. According to the results, the optimal condition oftemperature, time and mixing ratio was 400oC, 45min and 7:3 of sewage sludge/brewers grain, respectively. Theimpregnation of I is needed to keep the concentration of KI above 7%. I and Cl are dispersed uniformly in prepared adsorbent.

Compact fluorescent lamps are strongly encouraged to manage separately in Korea because Compact fluorescent lamps contain mercury. Compact fluorescent lamps have managed as household waste in Korea, however, even though Compact fluorescent lamps contains hazardous material such as mercury. The aim of management of Compact fluorescent lamps separately is to reduce the release of mercury from Compact fluorescent lamp lamps into the environment and to reuse of the glass, metals and other components of Compact fluorescent lamps. The amount of mercury in a fluorescent lamps varies, depending on the type of lamp and manufacturer, but typically ranges between 5 milligrams and 30 milligrams. The mercury content of fluorescent lamps has been reported to be between 0.72 and 115 mg/lamp with an average mercury content of about 30 mg/lamp in 1994. Although manufacturers have greatly reduced the amount of mercury used in fluorescent lamps over the past 20years, mercury is an essential component to fluorescent lamps and can’t be eliminated completely in lamps. In the crushing process, CFL(compact fluorescent lamp) is separated into glass, plastic, ballast, phosphor powder and vapor. Using the crushing technique, concentration of mercury vapor emission from CFL is evaluated. Through the experiments, the efficiency of the crushing and separation for the unit is estimated by measuring the volume of CFL. In this study, the concentration of mercury is analyzed by MVI(Mercury Vapor Indicator) method for vapor in CFL. From the results of mercury distribution for 3 companies, the concentration of mercury in compact fluorescent lamp is less than that in the other type lamps. And phosphor powder has greater than 99% of total mercury amount in CFL and the mercury concentration in phosphor powder is measured between 1,008ppm and 1,349ppm. The mercury concentration in phosphor powder can be changed by the type of company and period of usage. KET and TCLP are carried out for phosphor powder, glass, plastic, ballast and base cap to estimate the hazardous characteristic. From the results of KET and TCLP test for CFL, phosphor powder from CFL should be controlled separately by stabilization or other methods to reuse as a renewable material because the phosphor powder is determined as a hazardous waste. From the results of characteristics of CFL, the carbonization system of CFL should be carried out in the temperature of less than 350℃. The amount of mercury in a fluorescent lamps varies, depending on the type of lamp and manufacturer, but typically ranges between 5 milligrams and 30 milligrams. The mercury content of Compact fluorescent lamps has been reported to be between 0.72 and 115 mg/lamp with an average mercury content of about 30 mg/lamp in 1994. Although manufacturers have greatly reduced the amount of mercury used in fluorescent lamps over the past 20years, mercury is an essential component to fluorescent lamps and can’t be eliminated completely in lamps. In Korea, demonstration for recycling of U type lamps had once begun in the area of Seoul Metropolitan, 2000. In 2004, U type lamps was included as an item in EPR(Extended Producer Responsibility) system. According to Korea Lighting Recycling Association, approximately 38 million Compact fluorescent lamps were recycled in Korea, 2011 because 3 recycling facilities for Compact fluorescent lamps are operated in Korea. Recycling rate of Compact fluorescent lamps in Korea is about 31.0% but about 70% of Compact fluorescent lamps may not manage properly. Hence, discarded lamps release approximately 2 to 3 tons of mercury per year into the environment[6]. In USA, Compact fluorescent lamps has controlled by Universal Waste Rule and merchandises containing mercury prohibited to produce. Also, MEBA(Mercury Export Ban Act) is activated in USA from 2013. According to Association of Lighting and Mercury Recycler, member companies accomplish about 85% of the lamp recycling done each year. In Germany, best available technology (BAT) system for recycling of Compact fluorescent lamps is established and about 20 companies are involved in recycling of Compact fluorescent lamps. In 1994, approximately 70-80% of total Compact fluorescent lamps are recycled in 1994 and Compact fluorescent lamps was included as an item in EPR(Extended Producer Responsibility) system in 1996. In Sweden, MRT System, which was developed by Lumalampan, separated mercury from Compact fluorescent lamps by distillation operation, 1979. Reverse route collection system is active to improve the collection of Compact fluorescent lamps. Compact fluorescent lamps was included as an item in EPR(Extended Producer Responsibility) system in 2001. In Austria, about 40 companies are involved in recycling of Compact fluorescent lamps to recycle glass and ferrous metals. And wastes containing mercury are treated in landfill site by using special container [7,8]. In this study, Compact fluorescent lamps is cut by a end-cutting unit with a cam crusher and base-cap is separated from glass part. In the end-cutting unit, a vacuum system is operating to collect mercury vapor to prevent leaking from the end-cutting unit. First of all, characteristics and major composition of Compact fluorescent lamps are estimated. Through the experiments, it is measured mercury concentration in the parts of Compact fluorescent lamps such as glass tube, phosphor powder, and base cap after separation in the end-cutting unit. Also, it is evaluated mercury emission from Compact fluorescent lamps by measuring the concentration of effluent gas in the end-cutting unit with changing flow rate. Finally, Korea Extraction Method (KET) and TCLP(Toxicity Characteristic Leaching Procedure) test are applied to phosphor powder to verify that phosphor powder is a hazardous waste [9].

The response of the freshwater microalga Chlorella vulgaris to mercuric ion (Hg2+) stress was examined using chlorophyll a fluorescence image analysis and O-J-I-P analysis as a way to monitor the toxic effects of mercury on water ecosystems. The levels of photosynthetic pigments, such as chlorophyll a and b and carotenoids, decreased with increasing Hg2+ concentration. The maximum photochemical efficiency of photosystem Ⅱ(Fv/Fm) changed remarkably with increasing Hg2+ concentration and treatment time. In particular, above 200 μM Hg2+, considerable mercury toxicity was seen within 2 h. The chlorophyll a fluorescence transient O-J-I-P was also remarkably affected by Hg2+; the fluorescence emission decreased considerably in steps J, I, and P with an increase in Hg2+ concentration when treated for 4 h. Subsequently, the JIP-test parameters (Fm, Fv/Fo, RC/CS, TRo/CS, ETo/CS, ΦPO, ΨO and ΦEO) decreased with increasing Hg2+ concentration, while N, Sm, ABS/RC, DIo/RC and DIo/CS increased. Therefore, a useful biomarker for investigating mercury stress in water ecosystems, and the parameters Fm, ΦPO, ΨO, and RC/CS can be used to monitor the environmental stress in water ecosystems quantitatively.

Linear type SFL (spent fluorescent lamp) can be classified by 3-banded lamp and general lamp. Linear type SFL is separated by the end-cutting technique to examine the distribution of mercury in the major components such as base cap, glass part and phosphor powder. In this study, the concentration of mercury is analyzed by DMA (Direct Mercury Analysis) method for major components in linear type SFL. From the results of mercury distribution for 3 companies, the concentration of mercury in 3-banded lamp is less than that in general lamp. And phosphor powder has greater than 80% of total mercury amount in SFL and the mercury concentration in phosphor powder is measured between 1,250 ppm and 1,740 ppm. The mercury concentration in phosphor powder can be changed by the type of lamp, company, and period of usage. KET and TCLP are carried out for phosphor powder, glass, and base cap to estimate the hazardous characteristic. From the results of KET and TCLP test for general lamp and 3-banded lamp, phosphor powder from general lamp and 3-banded lamp should be controlled separately by stabilization or other methods to reuse as a renewable material because the phosphor powder is determined as a hazardous waste.

The objectives of this study were to measure ambient total gaseous mercury (TGM) concentrations in Seoul, to analyze the characteristics of TGM concentration, and to identify of possible source areas for TGM using back-trajectory based hybrid receptor models like PSCF (Potential Source Contribution Function) and RTWC (Residence Time Weighted Concentration). Ambient TGM concentrations were measured at the roof of Graduate School of Public Health building in Seoul for a period of January to October 2004. Average TGM concentration was 3.43±1.17 ng/㎥. TGM had no notable pattern according to season and meteorological phenomena such as rainfall, Asian dust, relative humidity and so on. Hybrid receptor models incorporating backward trajectories including potential source contribution function (PSCF) and residence time weighted concentration (RTWC) were performed to identify source areas of TGM. Before hybrid receptor models were applied for TGM, we analysed sensitivities of starting height for HYSPLIT model and critical value for PSCF. According to result of sensitivity analysis, trajectories were calculated an arrival height of 1000 m was used at the receptor location and PSCF was applied using average concentration as criterion value for TGM. Using PSCF and RTWC, central and eastern Chinese industrial areas and the west coast of Korea were determined as important source areas. Statistical analysis between TGM and GEIA grided emission bolsters the evidence that these models could be effective tools to identify possible source area and source contribution.