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TRANSPORT AND BIOACCUMULATION OF DIOXIN AND FURANES IN AQUATIC ENVIRONMENT NEAR BIEN HOA AGENT ORANGE HOTSPOT (VIETNAM)

Minh NH1, Nam VD1, Thuong NV1, Hue NTM1, Tuan NH1, Toan PH1, Son LK1,2
1 2

Dioxin Laboratory, Vietnam Environment Administration (Nr.556 Nguyen Van Cu, Hanoi, Vietnam) Office of National Steering Committee 33, Ministry of Natural Resources and Environment

Introduction Bien Hoa city is located in the west of Dong Nai province and about 35 km away from north of of Ho Chi Minh City (HCMC). During the U.S War in Vietnam, Bien Hoa airbase was used as one of major military bases for the Ranch Hand operation, which sprayed defoliants to destroy forest canopies and crops. Approximately 159,000 barrels of herbicides, including 98,000 barrels of Agent Orange, 45,000 barrels of Agent White and 16,000 barrels of Agent Blue were transported by US army to Bien Hoa airbase for this operation. In order to load herbicides conveniently, onto aircraft for air spraying, defoliants were firstly pumped into large 28,000 litter tanks. Spillages and leakages of defoliants (especially for Agent Orange) during 10 years of the operation caused extremely high contamination of dioxin in certain sites and thus making the airbase well known as one of AO hotspots1. Concerning adverse impacts of dioxin to local environment, human health and social condition, in 2006 the Government of Vietnam implemented a three-year project, which had target to contain the highest dioxin-contaminated area of about 4 hectares by secure landfill. However, it is a fact that other contaminated sites may still exist in this airbase2. They might be originally caused by spillages of AO during the war or caused by accumulation of contaminated soils which were washed out from heavily contaminated sites due to floods and rains. It is very important to clarify current contamination status so that further remediation activities can be accurately established. In this study, we carried out hydrological and topography surveys in order to identify potential low-land areas, lakes and ponds which can accumulate dioxin-contaminated soils washed out from heavily contaminated sites by floods and storm waters during the past 30 years. Basing on data of these field surveys, we collected low-land soil, surface sediment, core sediment, fish and duct samples from suspected areas for determination of dioxins and furans (PCDD/Fs). Result from this study is expected to identify further contaminated sites and to clarify transport and accumulation of AO/dioxin in local aquatic environment. Materials and methods Hydrological and topography surveys were done within the area of Bien Hoa Airbase. The results pointed out dominant directions of storm water as well as major reservoirs which receive storm waters and thus also accumulate dioxin-contaminated soils over the past decades. Figure 1 showed the primary AO contaminated site namely Z1 (which was actually contained in a secure landfill at present time) as well as other suspected AO secondary sites including low-land areas and ponds. In 2010, sediment, soil and fish samples were collected in Z1 Lake, low-land site near Z1 Lake, Gate II Lake, series of ponds and low-land areas in the west of the runway. Besides, sediment cores were also taken at two large lakes (Z1 and Gate II). Sediment samples (0-5cm) were collected by Erkman dredge; Sediment cores were collected by corer and divided into several segments of 5cm which is one individual sample (data not yet available). Fish were collected in ponds and lakes and muscle was taken for analysis of PCDD/Fs. A duck sample (muscle and liver) was also collected in the West ponds. PCDD/Fs in sediment and fish samples were determined by High Resolution Gas Chromatography coupled with High Resolution Mass Spectrometer (HRGC/HRMS). The procedures followed those described by Kannan et al. (2001)3. Briefly, 5 grams of dried sample was extracted for 18 hours by Sohxlet extractor using mixture of DCM/Hexane (20:80). The extract was passed through silica gen multi-layer column, activated carbon column for clean-up and separation of PCDD/Fs. Subsequently, the solution was concentrated under rotary vacuum evaporator and followed by evaporation under gentle nitrogen stream to final volume of 100 uL. Application of surrogates and internal standards follow those described in US EPA method 1613. The final solutions were injected in HRGC/HRMS for determination and quantification of PCDD/Fs. Seventeen most toxic dioxin and

furan compounds were analyzed and TEQ concentration was calculated following WHO-TEF (2005). For sediment, method quantification limits of HxCDDs and HpCDDs varied from 4.6 to 5.2 pg/g, while those for PeCDFs, HxCDFs and HpCDFs were between 3.2 4.2 pg/g.

Figure 1: Sampling sites in BH airbase for sediment and fish samples (Z1 Lake, G-2 Lake, Bien Hung Lake and Pond system in west of the airbase) Results and discussion Levels of PCDD/Fs in sediment and fish samples Concentrations of PCDD/Fs and TEQ in sediment and fish samples were given in Table 1. The concentrations for sediment were on dry weight basis and those for fish and duck samples were on wet weight basis. It is easily recognized that among PCDD/Fs congeners, TCDD (2,3,7,8-TCDD) is the dominant one on TEQ basis, its concentration is far above all the other in sediment and fish samples. TEQ in sediment samples ranged between 74 4860 pg/g with average level of 972 pg/g and median level of 650 pg/g. These are very high contamination levels and suggesting high contamination in these lakes and ponds. The highest PCDD/Fs levels were found in the West pond system (650 4860 pg/g) followed by Z1 lake, G-2 lake and Bien Hung Lake. In such sediment samples, contribution of TCDD to TEQ is normally between 92 and 100%, implying Agent Orange as the major source of TEQ. It was observed previously that soil in Z1 AO site showed extremely high level of TEQ (as much as hundreds ng/g TEQ) and also high contribution of TCDD2. However, it is first time to observe such wide spread of contamination and elevated PCDD/Fs levels in the West pond system which is far from known AO sites in Bien Hoa airbase. It is a surprise for us to find such higher PCDD/Fs level in the West pond system compared to Z1

Lake, considering that Z1 Lake locates very near the most contaminated site namely Z1. We therefore suggested that there might be more unidentified AO/Dioxin sites in the west of Bien Hoa airbase. In fact, at the beginning, our field surveys did not suggest any visual sign of highly AO/Dioxin contaminated site in the west area. However, when soil in some points of the west area were excavated down to 1-2m, sensible signs for AO remains such as smell of chemical and color of deep soil appeared. We highly suspected that AO/Dioxin contamination might still exist in deeper soil layer of this area. More investigations are very necessary to answer question whether high dioxin contamination might exist under the surface of this area? Nevertheless, according to standard guideline in Vietnam which stipulating a maximum level of 150 pg/g TEQ for PCDD/Fs in sediment4, Z1 Lake, G-2 Lake and the West ponds must be placed under consideration for remediating activities. On the other hand, Bien Hung Lake should be tightly kept under monitoring program. Level of TEQ in fish samples are also very high, ranging from 12 - 288 pg/g on wet weight basis. The highest level was found in a catfish collected from the West pond system and the lowest one found in a small tilapia in Z1 Lake. Comparison of TEQ in the fish samples might suggest that catfish (P17) accumulated much more dioxins than tilapia (P5, P16 and P22). Nevertheless, consumption of fish and duck from such lakes and ponds is not safe anymore and thus actions to raise awareness of local communities are needed immediately, especially for the area in west of the airbase. Table 1: Concentration of PCDD/Fs and TEQ in sediment samples (pg/g dry wt.) and fish samples (pg/g wet wt.) from Bien Hoa airbase
Sample code TCDD PeCDD S-HxCDDs HepCDD OCDD TCDF S-PeCDFs S-HxCDFs S-HpCDFs Z1 Lake P1 SeBH3 281 8.0 6.7 117 1140 23 ND ND 19 P2 SeBH9 505 14 39 383 4160 39 ND 5.9 43 P3 CoBH1 (5) 135 7.5 12 68.0 582 10 2.1 8.6 9.1 P4 CoBH2 (5) 993 21 24 201 1680 48 ND ND 23 P5 Fish-BH26 12 0.03 ND ND ND 1.6 ND ND ND West pond systems P6 BH12 1273 30 147 1532 10683 130 21 58 168 P7 BH14 4740 50 283 945 3360 351 5.8 15 46 P8 BH16 2080 37 131 821 6880 216 16 22 77 P9 BH19 1029 36 169 932 5595 174 13 33 88 P10 BH21 734 7.9 13 191 1960 113 ND ND 21 P11 BH22 622 9.2 19 346 3800 76 ND 12 48 P12 BH25 1340 19 71 442 3090 77 ND ND 22 P13 BH26 884 20 13 118 1570 49 ND ND 13 P14 BH27 1380 26 74 358 2290 79 ND ND 20 P15 BH28 401 6.5 ND 88.5 1690 20 ND ND ND P16 Fish-BH3 73.7 0.21 0.06 0.17 3.6 8.7 0.07 ND ND P17 Fish-BH9 286 1.82 3.5 0.77 ND 0.75 0.17 0.04 ND P18 Duck-BH2 35.4 0.52 1.0 0.77 ND 2.7 0.27 0.22 0.07 G-2 Lake P19 BH33 202 5.4 23 332 3730 12 ND 18 51 P20 BH36 230 10 45 606 8360 22 10 26 107 P21 CoBH4 (10) 443 18 29 227 1749 38 1.4 11 28 P22 Fish-BH27 15.6 0.13 ND ND ND 0.63 0.08 ND ND Bien Hung Lake P23 BH39 362 8.0 22 123 1438 32 1.4 9.4 15 P24 BH43 62 3.5 13 179 1820 19 ND 6.7 25 TEQ calculated followingTEF- WHO 2005; ND: level lower than detection limits (please refer text for details) PCDD/Fs are same as the seventeen compounds listed in WHO-2005 OCDF 50 136 20 68 ND 255 113 230 137 49 108 46 44 35 82 ND ND ND 169 477 51 ND 24 65 TEQ 297 536 147 1030 12 1361 4860 2160 1117 760 650 1380 916 1430 416 75 288 36 219 261 472 16 378 74

Homologue profile of PCDD/Fs in sediment Homologue profiles of PCDD/Fs are useful tool for assessment of chemical natures of each group in target media5. Figure 1 showed homologue profiles of tetra- through octa-CDD/Fs. These profiles were calculated basing on normal concentration and reflecting contribution of each homologue group to total concentration 5,6. It was observed that sediment showed consistent pattern for all sample groups, showing the most dominance of

OCDD followed by TCDD, HepCDDs, OCDF and TCDF. On the other hand, fish and duck samples showed the most dominance of TCDD followed by TCDF. Bioaccumulation of PCDD/Fs is quite selective for TCDD in this study. The pattern in biological samples was very unique and reflecting recent and acute exposure to dioxins from AO source which contains a lot of TCDD.
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Figure 1: Homologue profile of PCDD/Fs in sediment and biological samples from four studied sites (the vertical axis is percentage of PCDD/Fs homologues on pg/g basis) The present study has suggested wide spread of dioxin contamination in aquatic environment in Bien Hoa airbase, known as one of major AO hotspots in South Vietnam. The high levels of PCDD/Fs in sediment and fish samples collected in the local ponds and lakes are very much of concern and urge for remediation and intervention activities. Unidentified AO sites may exist in West of the airbase and thus continuous investigations will be needed for further clarification. Acknowledgements This study was implemented in the framework of Dioxin Laboratory Project funded by Ministry of Natural Resources and Environment (Vietnam), Bill & Melinda Gates Foundation, and the Atlantic Philanthropies. The authors would like to express sincerest thanks to Dr. Kurunthachalam Kannan (Wardwood Center, NY, USA) and Dr. Olaf Ppke (Eurofins Laboratories, Hamburg, Germany) for their useful discussion and kind support with cross checking analysis in their laboratory. References 1. Young AL. (2007); Presentation on historical usage of defoliants; Vietnam-U.S Joint Workshop: June 2007. 2. Minh NH, Son LK, Nguyen PH, Truong NX, Hoai PM. (2008); Organohalogen Compounds. 70: 000543546. 3. Kannan K, Kober JL, Kang YS, Masunaga S, Nakanishi J, Ostaszewski A, Summer CL, Giesy JP. (2001); Environ Toxicol Chem. 20: 1878-89. 4. TCVN (2009): Dioxins threshold in the soil and sediment, Nr. 8183:2009; 5. US EPA. 2001. Database of sources of environmental releases of dioxin and dioxin-like compounds in US. <http.//www.epa.gov/ncea/Dioxin_Database/> 6. Minh NH, Minh TB, Watanabe M, Kunisue T, Monirith I, Tanabe S, Sakai S, Subramanian A, Sasimumar K, Viet PH, Tuyen BC, Tana T, Prudente M. (2003); Environ Sci & Technol: 37(9): 1493-1502.

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