경기도 북부지역 군용 사격장 토양에 존재하는 화약물질 분포 및 이동 특성 조사

배범한(Bumhan Bae),박지은(Jieun Park) 한국지반환경공학회 2014 한국지반환경공학회논문집 Vol.15 No.6

경기도 OO지역 군 사격장에서 환경으로 유출되는 화약물질 현장저감시설의 설계 자료 확보를 위해 토양오염조사를 실시하였다. 설계에 필요한 자료는 (i) 주 오염 화약물질 종류 파악, (ii) 배출/이동 경로, (iii) 토양 입경별 화약물질 농도조사 및 침강특성이다. 현장 조사 및 분석결과, TNT와 RDX가 사격장 토양에서의 주 오염물질이지만, 군 훈련 종류와 사격장 지형에 따라 오염도는 변화하였다. 화약물질은 표토이외의 심토와 인근 개울에서도 검출되어, 피탄지에서 하천으로의 유출이 있음을 확인하였다. 피탄지에 화약물질 농도가 높은 hot spot이 다수 존재하였으나, 전반적으로 오염농도가 20 mg/kg을 넘지는 않았다. 피탄지 토양 내 점토함량은 대조군 12 %에 비해 현저히 낮은 5 % 미만이며, 이는 사격으로 인해 식피가 제거되어 강우 시 토사의 표면유출이 증가하였기 때문이라 판단된다. 토양 입경별 화약물질 분포 분석 결과, 토양 입경 0.075 mm 미만의 세립토에는 화약물질 총량의 약 10 % 이하만이 존재하였다. 침강관 실험결과, 유출수 내 액상으로 유출되는 화약물질량이 고상에 있는 화약물질량보다 많았다. 그러므로 사격장에서 표면 유출되는 강수 내 입자상 물질을 간단한 침전지로 처리하고, 다음으로 정화식물을 식재한 인공습지로 액상 내 화약물질을 처리하는 방안이 자립적이며 지속적으로 유지 가능한 녹색 정화방법이 될 것이다. A remedial investigation was conducted at five military training ranges in northern Gyeonggi province to collect information necessary for the design of on-site treatment facilities for the abatement of explosive compounds release to the environment. These information includes (i) identification of dominant explosive compounds in each range, (ii) discharge/migration routes, and (iii) contaminant distribution in particle size fraction and settling velocity of the soils. The results of investigation showed that TNT and RDX are the major contaminants but the extent of contamination varied depending on the types of military training practices and topography of the site. RDX was also detected in the subsurface soil and in the nearby stream within the training ranges, suggesting release of contaminants to streams. The median concentrations of explosives in the surface soil were less than 20 mg/kg despite several ‘hot spots’ in which explosives concentrations often exceeds several hundred mg/kg. The average clay contents in the soil of target area was less than 5 % compared to 12 % in the control, indicating loss of smaller particles by surface runoff during rainfall due to lack of vegetative land cover. Analysis of explosive compounds and particle size distribution showed that the amount of explosive compounds in soil particles smaller than 0.075 mm was less than 10 % of the total. Settling column tests also revealed that the quantity of explosive compounds in the liquid phase of the effluent was greater than that in the solid phase. Therefore, pre-treatment of particulate matter in surface runoff of shooting range with a simple settling basin and subsequent effluent treatment with planted constructed wetlands as polishing stage for explosives in the aqueous phase would provide the shooting ranges with a self-standing, sustainable, green solution.

화약물질 현장검출시약 EXPRAY$^{(R)}$를 이용한 토양내 화약물질 스크리닝 및 준정량화 가능성

배범한,조정현,Bae, Bum-Han,Cho, Jung-Hyun 한국지하수토양환경학회 2009 지하수토양환경 Vol.14 No.2

A quick and simple detection method of explosive compounds in environmental matrix (soil and water) can provide a screening step which reduces the number of unnecessary samples and the cost of expensive laboratory analysis at a site investigation. A commercially available EXPRAY$^{(R)}$Explosives Field Detection Kit (EXPRAY) was used to determine the minimum detection concentration and to test the possibility of semi-quantitative analysis of 14 explosive compounds using standard solutions. The results showed that EXPRAY could detect 5 explosive compounds, TNT, RDX, HMX, Tetryl, and TNB, out of 14 US EPA designated explosives. The minimum detection limit of the nitramine explosives was 14 ng/$^2$ for HMX and RDX. EXPRAY was more sensitive to nitroaromatics than the nitramines and the minimum detection limits per unit area (mm$^2$) for Tetryl, TNB, and TNT, were 3 ng, 3 ng, and 0.3 ng, respectively. The semi-quantification of 5 explosive compounds in an order ofmagnitude could be achieved by the intensity of developed color only when EXPRAY was applied on the standard solutions under controlled laboratory conditions. With contaminated soil samples, however, only the presence and type of explosive compounds was identified. Therefore, EXPRAY is an economic and sensitive method that can be used in a screening step for the identification of explosives in the field samples. 환경 시료 (토양 및 수질)내 화약물질을 신속하고 간편하게 검출할 수 있다면, 현장조사에서 오염도 조사를 위한 스키리닝 단계로 이용하여 불필요한 시료의 갯수와 고가의 실험실 정량분석비용을 줄일 수 있다. 상용 EXPRAY$^{(R)}$ Explosives Field Detection Kit(EXPRAY)를 이용하여 14종의 화약물질을 대상으로 화약물질 표준용액에 대한 최저검출농도를 결정 하고 및 준정량화 가능성을 확인하기 위한 실험을 실시하였다. 실험결과 EXPRAY는 14종의 화약물질 중에서, TNT, RDX, HMX, Tetryl및 TNB등 5종의 화약물질을 검출할 수 있었다. Nitramine계열인 HMX와 RDX에 대한 최저검출농도는 모두 14ng/mm$^2$이었다 EXPRAY는 nitroaromatic계열에는 더욱 민감하게 반응하여, Tetryl, TNB및 TNT에 대한 단위면적당(mm$^2$)최저 검출량이 각각 3ng, 3ng및 0.3ng이었다. 실험이 통제되는 조건에서 화약물질 표준용액에 EXPRAY를 적용하였을 경우에는 발색 강도의 비교를 통해 10배 단위의 준정량화가 가능하였다. 그러나 오염토양으로 실험한 경우에는 화약물질의 존재여부 및 종류만을 확인할 수 있었다. EXPRAY Explosives Detection Kit$^{(R)}$가 화약물질을 검출할 수 있는 경제적이고 민감한 방법이지만, 현장시료의 스크리닝 단계에만 적용할 수 있는 방법이다.

HPLC에 의한 토양내 화약물질 정량분석조건 최적화

조정현,배범한,김계훈,Cho, Jung-Hyun,Bae, Bum-Han,Kim, Kye-Hoon 한국지하수토양환경학회 2009 지하수토양환경 Vol.14 No.1

HPLC에 의한 토양내 화약물질의 분석 방법을 최적화하기 위해 현재 실사격 훈련이 진행 중인 군사격장 2곳에서 토양시료를 채취하여 분석 실험을 수행하였다. 토양과 오염물질의 불균일도를 감안하여 segregation constant 와 homogeneity constant를 기준으로 산정한 결과, 화약물질의 분석을 위한 토양시료채취 최소량은 125g 이었다. 그리고 시료 전처리 과정인 추출단계에서 필요한 적정시료량과 추출액의 비율을 CV값에 근거하여 산정한 결과 토양 10g/ACN 20 mL가 가장 효과적이었다. 미국 EPA에서 지정한 화약물질 14종을 모두 분리하기 위한 HPLC의 용리 조건은 RP C18캘럼을 이용하여 칼럼온더 30${\circ}C$일 때, 이동상 구성 및 유량은 isopropanol : acetonitrile : water의 비율 18 : 12 : 70, 유량 0.80mL/min인 경우가 최적이었다. 분석파장 결정을 위해 분석 파장 230nm와 254nm에서의 화약물질 14종에 대한 검출한계 (detection limit)값과 각 화약물질의 UV/VIS스펙트럼을 비교한 결과 254nm보다 230nm일때가 더 적절하였다. 하지만 NB, 2,4-DNT, 2NT, 4NT및 3NT는 분석파장이 UV254nm일때 더 적절하였다. A series of experiments was performed to develop an optimized analytical procedure for the analysis of explosives in soil by HPLC with soil samples collected at two live-fire military shooting ranges. The minimum amount of soil to be collected, Wmin, for the analysis of explosive compounds was 125g, based on the segregation and homogeneity constants that account for soil heterogeneity and non-homogeneous distribution of target explosive compounds. The optimization of extraction and HPLC analytical conditions were also studied based on analytes CV values. The most effective soil/ extractant ratio was estimated to be 10g-pretreated soil/20 mL acetonitrile as extractant. The optimized HPLC elution conditions for the separation of US EPA designated 14 explosive compounds, were column temperature 30${\circ}C$, eluents ratio of isopropanol: acetonitrile: water = 18 : 12: 70, and flow rate of 0.8 mUmin at 230 nm. However, UV wavelength 254 nm was better for the analysis of NB, 2,4-DNT, 2NT, 4NT, and 3NT.

트리나이트로이미다졸 치환체들의 화약성능 및 감도 예측 분석

전영진,김현수,김진석,조수경,Jeon, Yeongjin,Kim, Hyoun-Soo,Kim, Jin Seuk,Cho, Soo Gyeong 한국군사과학기술학회 2017 한국군사과학기술학회지 Vol.20 No.4

Various chemical properties including density and heat of formation of 1-substitued trinitroimidazoles (TNIs) were estimated by using density functional theory (DFT). Using chemical properties estimated by DFT, explosive performance and sensitivity of 1-substitued TNIs were analyzed by following the ADD Method-1 procedure. The results were displayed on two-dimensional performance-sensitivity plot, and were compared with those of explosive molecules commonly used in many military systems. Different 1-substituents of TNI made that both explosive performance and impact sensitivity were changed significantly. Methyl substituted TNI became moderately insensitive and slightly less powerful. Amino, fluoro, picryl, and difluoroamino substituted TNIs were highly powerful like RDX and HMX, but greatly sensitive. Nitro substituted TNI was predicted to be extremely sensitive to be handled as a secondary explosive.

디메틸포름아마이드 용매와 초임계 이산화탄소 역용매를 사용한 RDX 고에너지 물질의 재결정

김창기(Chang-Ki Kim),이병철(Byung-Chul Lee),이윤우(Youn-Woo Lee),김현수(Hyoun-soo Kim) 한국청정기술학회 2009 청정기술 Vol.15 No.4

수경재배조건에서 다년생 벼과식물(물억새 및 갈풀)에 의한 RDX 흡수 및 분해

박지은(Ji Eun Park),배범한(Bum Han Bae) 大韓環境工學會 2014 대한환경공학회지 Vol.36 No.4

경기도 북부에 위치한 3개 사격장 식생조사를 통해 우점 식물인 물억새와 갈풀을 수경재배조건에서의 RDX 흡수실험대상 식물로 선정하였다. 화약물질 비오염토에서 재배한 두 종 식물의 유식물을 사용하여 대조군, 무처리군 및 RDX 농도 10, 20, 30 및 40 mg/L인 1/4 Hoagland 용액에서 4배수로 수경재배하였다. 실험기간 15일 동안 배양액을 주기적으로 채취하여 pH와 RDX 농도를 관측하고, 실험이 종료된 다음에는 식물체 내 RDX를 추출하여 지상부 및 지하부 내 함량을 측정하였다. RDX에 노출된 기간 동안, 두 종의 식물에서 RDX에 의한 어떤 식물독성도 보이지 않았다. RDX에 대한 유사1차반응 제거상수는 물억새와 갈풀에서 각각 0.0143~0.0484 day-1 and 0.0971~0.1853 day-1의 범위이었다. 식물체량에 평균화한 RDX 제거 상수는 RDX 초기농도에 따라 감소하였고, 물억새와 갈풀에서 각각 0.27~1.01 mL·g-1day-1 and 0.87~1.66 mL·g-1day-1의 범위에 있는 것으로 산정되었다. 처리 15일 후, 물억새 처리구에서 반응조 용액 내 RDX 제거비율은 초기 RDX 농도가 증가함에 따라 49.0%에서 23.7%로 감소하였고 평균 7.3%의 RDX는 식물체내 잔류하였다. 갈풀을 식재한 반응조에서 초기 RDX량의 16.8% 및 5%가 각각 반응조 내 용액과 식물체에 잔류하였다. 물억새에서는 발견되지 않았던 미확인 극성물질이 갈풀 지상부 및 지하부에서 다량 검출되었다. Amur silver grass (Miscanthus sacchariflorus) and reed canary grass (Phalaris arundinacea) were selected for RDX removal experiments in hydroponic culture conditions based on vegetation survey at three shooting ranges in northern Kyunggi province. Seedling of two plants were grown in 1/4 strength Hoagland solution in quadruplicates containing 10, 20, 30, 40 mg/L RDX for 15 days along with control and blank treatments. During the 15 days of incubation, pH and RDX concentration in medium were routinely analyzed and RDX contents in the shoot and the root were determined after solvent extraction at the end of the experiments. Both plant species showed no symptoms of RDX phyto-toxicity. The pseudo first order RDX removal constants for amur silver grass and reed canary grass were in the range of 0.0143~0.0484 day-1 and 0.0971~0.1853 day 1, respectively. Plant biomass normalized RDX removal rates, which decreased with the increase of initial RDX concentration, were in the range of 0.27~1.01 mL·g-1day-1 and 0.87~1.66 mL·g-1day-1 for amur silver grass and reed canary grass, respectively. After 15 days of treatment, RDX removal from the medium decreased from 49.0% to 23.7% with increase in the initial RDX concentration in amur silver grass and 7.3% of the initial RDX remained in the plant. In reed canary grass planted medium, less than 16.8% and 5% of the initial RDX remained in the medium and in the plant, respectively. Large quantities of unidentified polar compound, which was not detected in amur silver grass, accumulated in the root and shoot of reed silver grass.

포탄 사격장 토양의 RDX에 의한 인근 하천 오염 예측

박정태,이동수 한국군사과학기술학회 2019 한국군사과학기술학회지 Vol.22 No.6

Recently, pollution from gunpowder due to shell shootings at military drilling sites has raised various environmental concerns. The purpose of this study is to predict the contamination level of RDX in the soil area of the firing range zone near Anwol river watershed, the study site, and the intake area, Anwol river and Imjin river, as a function of time and space. In this study, a multimedia model was developed to predict the variation of RDX contamination by rainfall. The range of the medium was limited to soil, water, and sediment, and excluded the atmosphere, taking into account the physical and chemical properties of RDX with low vapor pressure and low Henry’s constant. The pollutant levels of the waters of compartments, including the last section of the Imjin River affecting the water intake, was compared with the environmental standard for RDX.

토착 야초류(어저귀, 자귀풀)의 수경재배를 이용한 Hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX) 분해 연구

배범한(Bae Beom Han),권영석(Kwon Yeong Seog),김동일(Kim Dong Il),이인숙(Lee In Sug),정연규(Jeong Yeon Gyu) 大韓環境工學會 2003 대한환경공학회지 Vol.25 No.9

분자화약 TNAZ 합성에 대한 개선 기법

전용구 한국군사과학기술학회 2003 한국군사과학기술학회지 Vol.6 No.1

TNAZ is a high explosive material because it is a highly strained ring compound containing one nitramine and gem dinditro groups. 1-t-butyl-3-nitroazetidine which was used as an intermediate previously, which declined the overall yield in synthesizing TNAZ. We obtained 1-t-butyl-3-hydroxymethyl-3-nitroazetidine in 64% yield from advances process which was used in synthesis of 1-t-butyl-3-nitroazetidine. The reaction pathway, shortening of reaction time, together with improvement of yield were studied too. We have obtained TNAZ in 85% yield.