Colloid facilitated transport of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to the groundwater at Ma Da Area, Vietnam

PCDD/Fs are hydrophobic organic substances and strongly sorbing to soil particles. Once adsorbed to soil particles they are believed to be virtually immobile. However, research in the last decades confirmed that strong sorbing contaminants may reach the groundwater via colloid-facilitated transport. This pathway has not been investigated before in Vietnam. Ma Da area, 100 km north of Ho Chi Minh City, was repeatedly sprayed during the Vietnam War (1962–1971) with herbicides like Agent Orange containing, beside others, the teratogenic contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 11 surface soil samples and 12 water samples were collected in Ma Da area for analysis of PCDD/Fs in solids. Soil TCDD concentrations ranged from 1–41 ppt with a mean of 8.8 ppt and a mean I-TEQ of 9.7 ppt. Two surface water samples showed colloid bound TCDD (7 and 19 ppt). Groundwater samples showed elevated colloid bound PCDD concentrations (mean 770 ng/kg), mainly octachlorodibenzo-p-dioxin. Groundwater colloids separated by filtration did not show any TCDD. The results support that TCDD/Fs can be relocated from the top soil to the groundwater by colloidal pathway. They did not provide evidence that the dioxins bound to groundwater colloids are leftovers from the Second Indochinese War. However, this study reinforces that the colloidal transport pathway has to be included investigating the relocation of strong sorbing organic contaminants.     

Levels of dioxins and dibenzofurans in breast milk of women residing in two cities in the Irkutsk Region of Russian Siberia compared with American levels

The presence of dioxins, dibenzofurans, and polychlorinated biphenyls (PCBs) in human tissue, food, and environmental samples from Russia has been monitored since 1988 as part of a research collaboration between a number of countries including Finland, the United States, Germany, the former Soviet Union, and Canada. Although elevated TCDD and PnCDD levels have previously been found in blood of male and female Russian chemical manufacturing workers and in their children, dioxin levels in the general population have usually been found to be lower than in Americans and Europeans. This study continues earlier work in the Irkutsk region of Russian Siberia, where we report levels of dioxin, dibenzofurans, and PCBs in human milk samples taken from general population women living in the industrialized cities of Angarsk and Usolye-Sibirskoye, near Lake Baikal. Total polychlorinated dibenzo-p-dioxin (PCDD) toxic equivalents (TEQs) compared in this paper for the industrialized regions of Siberia, Ukraine, and the US are similar, ranging from 6.1 to 7 parts per trillion (ppt). Recent 1998 milk samples from Angarsk and Usolye-Sibirskoye have total mean polychlorinated dibenzofuran (PCDF) TEQs of 10 and 21.7 ppt, respectively, with the other industrialized countries ranging from 2.3 to 6.7 ppt. Although dioxin-like PCBs were not measured for the city of Usolye-Sibirskoye (1998), total mean PCDD/F TEQ from Angarsk and Usolye-Sibirskoye (1998) were the two highest levels in this study, with 26.9 and 28.5 ppt, respectively, followed by 1993-1994 Ukraine samples with 24 ppt, 1989 Siberian samples with 13.6 ppt, and 1996 USA with 11.4 ppt total TEQ. In this study, higher levels of dioxins are noted in milk from Angarsk and Usolye-Sibirskoye than found in earlier Russian studies, with mean levels also exceeding 1996 and 1999 US breast milk dioxin levels.     

Receptor-mediated in vitro bioassay for characterization of Ah-R-active compounds and activities in sediment from Korea

Sediment extracts of stream sediments, collected from inland areas of Lake Shihwa (LSI) and Masan Bay (MBI), were screened for their abilities to induce aryl hydrocarbon receptor (Ah-R) mediated gene expression in vitro. Cell viability assay was also performed to examine cytotoxic effects on the Ah-R-mediated activities of sediment samples. Over 80% (30 out of 36) of sediment raw extracts (REs) induced significant Ah-R-mediated activities in the H4IIE-luc cell bioassays. Ah-R-mediated activities of sediment REs from LSI locations (mean=58%-TCDD-max; n=21) were greater than those of sediment REs from MBI locations (mean=35%-TCDD-max; n=15), in general. Seven (mean+/-SD=100+/-14%-TCDD-max) of 21 sediment REs from LSI showed Ah-R-mediated activities comparable to that (set to, 100%-TCDD-max) elicited by 1240 pM TCDD. Whereas, in MBI, only two REs from M1 (93%-TCDD-max) and M9 (82%-TCDD-max) showed significantly great responses that comparable to maximum response of TCDD standard curve. Sample potencies relative to the TCDD standard (TCDD-EQs) were estimated based on full dose-response characteristics of REs and TCDD-EQs were found to be 14-868 pg TCDD/g, dw and 17-275 pg TCDD/g, dw, in LSI and MBI, respectively. A range of TCDD-EQ20-80 of samples, based on multiple estimates of relative potency (REP20-80), did not vary greatly (2-4-fold) in the H4IIE-luc bioassays, which indicated relatively low degree of uncertainties in point estimates of REP for sediment REs examined. Acid-treatment of REs samples improved quantitative biological responses of samples followed by decreases in cytotoxicity identified by MTT cell viability assays.     

Chlorinated dibenzo-p-dioxin and dibenzofuran levels in human adipose tissue and milk samples from the north and south of Vietnam

Although 2,3,7,8-TCDD has been found to be extremely toxic to a variety of laboratory aminals, human epidemiology studies, where exposure to 2,3,7,8-TCDD has been less well characterized than in animal toxicologic studies, have been less conclusive in characterizing the extent of toxicity. In order to determine whether the newly refined techniques of human adipose tissue biopsy including isomer specific and sensitive measurement of PCDDs and PCDFs might be able to assist in finding populations within the same country with high and low levels of dioxins, adipose tissue samples were taken and levels analyzed from the north and south of Vietnam. It seemed reasonable, based on previous work, that high levels of 2,3,7,8-TCDD might still be found in adipose tissue in selected patients living in areas sprayed with Agent Orange and other 2,3,7,8-TCDD containing herbicides, and that lower levels should be found in patients not exposed to 2,3,7,8-TCDD from herbicides or other sources, such as persons who had always resided in the north of Vietnam. Of 9 specimens from patients hospitalized in Hanoi who had never been south, none had detectable adipose tissue levels of 2,3,7,8-TCDD at a detection limit of 2 or 3 ppt on a wet weight basis. Of 15 specimens from Ho Chi Minh City hospitalized patients the mean of positive specimens (12 of 15) was 28 on a lipid basis. The mean of the positive values from the south is about 2 to 3 times higher than found in the North American Continent control patients where the mean is about 6–10 ppt and much higher than in the north of Vietnam. In the northern specimens, the levels were non-detectable with a sensitivity of between 2 and 3 ppt. Other PCDD and PCDF isomers not found in Agent Orange, the penta- through octachlorinated dibenzo-dioxins and dibenzofurans, were similar in isomer type and quantity in the south of Vietnam to what we previously reported in North America. Adipose tissue from the north of Vietnam contained the lowest levels of four through eight chlorinated dioxins and furans thus far reported. The initial data suggests that populations exist in the south of Vietnam with elevated levels of 2,3,7,8-TCDD at the present time, fourteen years after the last known 2,3,7,8-TCDD (Agent Orange) application, superimposed on a preexisting body burden of dioxins and dibenzofurans from sources other than Agent Orange such as technical grade pentachlorophenol or products of incineration contaminated with higher chlorinated PCDDs or PCDFs. In light of the recent finding that unexpected levels of PCDDs and PCDFs exist in the general adult population of industrialized countries, ca. 1,000 to 1,200 ppt, wet weight of total dioxin and furan isomers in adipose tissues, it seems reasonable that the extent of human toxicity of dioxins may be more readily characterized in Vietnam than in industrialized countries. Because 2,3,7,8-TCDD was applied in 1962–1970, although not yet cleaned up, the levels of 2,3,7,8-TCDD in the environment, the food chain, and in humans, would be expected to decrease with time. Therefore, if studies are not initiated in a timely fashion, the opportunity to better characterize the extent of the toxicity of TCDD to humans as well as the persistence of TCDD in the environment in Vietnam may be lost.     

Tetrachlorodibenzo-p-dioxins and tetrachlorodibenzofurans in Atlantic coast striped bass and in selected Hudson River fish,waterfowl and sediments

In striped bass samples from the lower Hudson River and its estuary 2,3,7,8-tetrachlorodibenzo-$\text{p}$-dioxin (2,3,7,8-TCDD) was found at concentrations from 16 to 120 pg/g (ppt). Striped bass from two other locations (Rhode Island coastal waters and Chesapeake Bay, Maryland) had <5 ppt, 2,3,7,8-TCDD. The contaminant, 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF), was found in striped bass from all three locations with concentrations varying from 6 ppt in Chesapeake Bay to 78 ppt in the Hudson River. Results from a limited number of non-migratory fish (carp and goldfish) and sediments suggest that the upper Hudson River is not a source for 2,3,7,8-TCDD/2,3,7,8-TCDF contamination of striped bass.     

Assessing potential risks to wildlife and sportsmen from exposure to dioxin in pulp and paper mill sludge spread on managed woodlands

Potential human and wildlife exposures to TCDD in landspread pulp and paper mill sludge in the State of Maine were evaluated by means of a human health and an ecological risk assessment methodology. The highest historical concentrations of TCDD reported for these sludges do not present a risk to American woodcock, selected as an indicator species for this analysis. Concentrations of TCDD as high as 50 ppt in soil are not likely to produce adverse effects in the embryonic/hatchling stage of the woodcock. This soil concentration of TCDD does not present a significant risk to sportsmen and their families that may consume birds which inhabit these sites.     

Polychlorinated dibenzodioxins and polychlorinated dibenzofurans in sewage sludges

A municipal sewage sludge from Syracuse, New York and a largely domestic sludge from Sodus, New York were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) using combined gas chromatography and high resolution mass spectrometry (GC/HRMS). Concentrations in ppt of the following PCDDs were found in the syracuse sludge: tetrachlorodibenzo-p-dioxins (TCDDs), 150, hexachlorodibenzo-p-dioxins (HxCDDs), 2100, heptachlorodibenzo-p-dioxins (HCDDs), 6300, octachlorodibenzo-p-dioxins (OCDDs), greater than 60,000. The following ppt concentrations were found in the Sodus sludge: TCDDs, 7200, HxCDDs, 300, HCDDs, 900, OCDDs 7500. The TCDD was a single but not the highly toxic 2,3,7,8-isomer. PCDFs were mostly nondetectable in the sludges. The toxicology and potential for environmental contamination by these compounds are discussed.     

Levels of PCDDs, PCDFs and non-ortho PCBs in serum samples of non-exposed individuals living in Madrid (Spain)

In an attempt to evaluate the background levels of PCDDs, PCDFs and non-ortho PCBs in people living in Madrid (Spain), blood serum samples had been analyzed PCDD, PCDF and coplanar PCB levels from non exposed individuals are reported in this study. Average levels found were 515.29 ppt for total PCDDs, 66.73 ppt for total PCDFs and 85.47 ppt for non-ortho PCBs on a lipid weight basis Calculated I-TEQ values were 8.78 ppt for PCDDs, 6.96 for PCDFs and 7.03 for coplanar PCBs on a lipid weight basis.     

Seveso Women's Health Study: a study of the effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin on reproductive health

Although reproductive effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) exposure have been reported in numerous investigations of animals, studies of this association in humans are limited. In 1976, an explosion in Seveso, Italy exposed the surrounding population to among the highest levels of TCDD recorded in humans. The relatively pure exposure to TCDD and the ability to quantify individual level TCDD exposure from sera collected in 1976 for the Seveso cohort affords a unique opportunity to evaluate the potential dose-response relationship between TCDD exposure and a spectrum of reproductive endpoints. The Seveso Women's Health Study (SWHS) is the first comprehensive study of the reproductive health of a human population exposed to TCDD. The primary objectives of the study are to investigate the relationship of TCDD and the following endpoints: (1) endometriosis; (2) menstrual cycle characteristics; (3) age at menarche; (4) birth outcomes of pregnancies conceived after 1976; (5) time to conception and clinical infertility; and (6) age at menopause. Included in the SWHS cohort are women who were 0-40 yr old in 1976, who have adequate stored sera collected between 1976 and 1980, and who resided in Zones A or B at the time of the accident. All women were interviewed extensively about their reproductive and pregnancy history and had a blood draw. For an eligible subset of women, a pelvic exam and transvaginal ultrasound were conducted and a menstrual diary was completed. More than 95% of the women were located 20 yr after the accident and roughly 80% of the cohort agreed to participate. Data collection was completed in July 1998, serum TCDD analysis of samples for analysis of endometriosis as a nested case-control study was completed in October 1998, and statistical analysis of these data should be completed in early 1999. Serum samples are now being analyzed in order to relate TCDD levels with the remaining reproductive outcomes.     

Analysis of snake tissue and snake eggs for 2,3,7,8-tetrachlorodibenzo-p-dioxin via fused silica GC combined with atmospheric pressure ionization MS

Several snake tissue samples and one set of snake eggs were collected and analyzed for 2,3,7,8-tetrachlorodibenzo-$\text{p}$-dioxin. The isomer-specific analysis was performed using fused silica GC combined with atmospheric pressure ionization MS. The results ranged from a low of 38 parts-per-trillion (ppt) to high levels over 500 ppt.     

Dioxin reservoirs in southern Viet Nam--a legacy of Agent Orange

In the isolated Aluoi Valley of central Viet Nam, very high levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) were measured in soil, fish fat, duck fat, pooled human blood and breast milk samples collected from A So village between 1996 and 1999. The village was situated on a former military base occupied by US Special Forces between 1963 and 1966. TCDD was a contaminant of the herbicide "Agent Orange", aerially sprayed in the valley between 1965 and 1970, and stored at the A So base. Measured levels were lower near the sites of two other former US bases in the valley which had been occupied for shorter periods of time. In areas where Agent Orange had been applied by low-flying aircraft, levels of TCDD in soil, food and human samples were elevated, but lower than those near the three former US bases. We confirm the apparent food chain transfer of TCDD from contaminated soil to cultured fish pond sediments to fish and duck tissues, then to humans as measured in whole blood and breast milk. We theorize that the Aluoi Valley is a microcosm of southern Viet Nam, where numerous reservoirs of TCDD exist in the soil of former military installations south of the former demilitarized zone. Large quantities of Agent Orange were stored at many sites, used in ground and aerial applications, and spilled. TCDD, through various forms of soil disturbance, can be mobilized from these reservoirs after decades below the surface, and subsequently, introduced into the human food chain.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in marine mammals in the Canadian North

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in pooled samples of ringed seal (Phoca hispida) blubber, beluga (Delphinapterus leucas) blubber and polar bear (Ursus maritimus) liver and fat from several areas throughout the Canadian north and compared to mean PCB and HCB levels in the same samples. All seal samples, and all but one polar bear sample, had detectable 2,3,7,8-TCDD at concentrations ranging from 2 to 37 ng/kg, but TCDD was not found in beluga blubber (< 2 ng/kg). All seal samples and one of three beluga samples contained 2,3,7,8-TCDF at levels of 2 to 7 ng/kg, but TCDF was not found in any bear sample. TCDF must therefore be cleared rapidly by polar bears. No other PCDF congeners were found at detection limits of 4 to 8 ng/kg. OCDD concentrations in seal blubber and polar bear samples ranged from not detected (< 8 ng/kg) to 43 ng/kg. No apparent biomagnification of TCDD, OCDD or TCDF occurred from seal to bear fat, similar to previous findings for DDT, and unlike SigmaPCBs and HCB which biomagnified 6- to 17-fold. Highest concentrations of 2,3,7,8-TCDD and OCDD in seals and bears were found in the central Canadian Arctic Archipelago, and lowest were found in Hudson Bay, the reverse of PCB concentration distribution. The reason for higher levels of TCDD and OCDD in the Arctic than in the sub-Arctic is suggested to be trans-polar movement of aerosols with combustion-related origins in Eurasia. Levels of 2,3,7,8-TCDF were more evenly distributed throughout the North, and were positively correlated with PCB, but not with HCB or 2,3,7,8-TCDD levels in seals.     

Contamination of fish by 2,3,7,8-tetrachlorodibenzo-P-dioxin: A survey of fish from major watersheds in the United States

A survey of contamination of fish from major watersheds in the United States by 2,3,7,8-TCDD has been conducted by the U.S. EPA. Bottom feeding and predator fish were collected at 90 statistically selected and 305 regionally selected sites and analyzed by GC/MS. It was found that 19% of the statistically sampled sites and 31% of the regionally selected sites were contaminated at or above a minimum level of detection varying from 0.5 to 2.0 pg/g. Ten percent of all samples were contaminated at levels greater than 5.0 pg/g. It was also observed that a subset of samples collected at sites near discharge from pulp/paper manufacture (N=28) had a higher frequency of TCDD contamination above 5.0 pg/g (38%). This subset of samples also contained the sample of the greatest level of TCDD contamination (85 pg/g).     

Long overlooked historical information on agent orange and TCDD following massive applications of 2,4,5-t-containing herbicides,eglin air force base,sFlorida

BACKGROUND: From 1961-1971, The Air Development Test Center, Eglin Air Force Base (AFB), Florida, developed, tested, and calibrated the aerial spray systems used in support of Operation RANCH HAND and the US Army Chemical Corps in Vietnam. Twenty major test and evaluation projects of aerial spray equipment were conducted on four fully instrumented test grids, each uniquely arrayed to match the needs of fixed-wing, helicopter, or jet aircraft. Each of the grids was established within the boundary of Test Area 52A of the Eglin Reservation. METHODS: The tests, conducted under climatic and environmental conditions similar to those in Vietnam, included the use of the military herbicides (Agents) Orange, Purple, White, and Blue. Approximately 75,000 kg of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and 76,000 kg of 2,4-dichlorophenoxyacetic acid (2,4-D) were aerially disseminated on an area of less than 3 km2 during the period 1962-1970. Data from the analysis of archived samples suggested that an estimated 3.1 kg of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), present as a contaminant, were aerially released in the test area. Because most of the vegetation had been removed before establishing the test site in 1961, there was an opportunity to follow ground-based residues independent of canopy interception, and the resulting high solar exposure of initial residues. Studies of the soils, fauna, flora, and aquatic ecosystems of the test grids and associated perimeters of Test Area C-52A (an area totally more than 8 km2) were initiated in 1969 and concluded in 1984. RESULTS AND DISCUSSION: Data from soil samples collected from 1974 through 1984 suggested that less than one percent of the TCDD that was present in soil when sampling began persisted through the ten-year period of sampling. More than 340 species of organisms were observed and identified within the test area. More than 300 biological samples were analyzed for TCDD and detectable residues were found in 16 of 45 species examined. Examination of the ecological niches of the species containing TCDD residues suggested each was in close contact with contaminated soil. Indepth field studies, including anatomical, histological and ultrastructural examinations, spanning more than 50 generations of the Beachmouse, Peromyscus polionotus, demonstrated that continual exposure to soil concentrations of 0.1 to 1.5 parts-per-billion (ng/g) of TCDD, had minimal effects upon the health and reproduction of this species. CONCLUSIONS: Since Agent Orange with its associated TCDD contaminant was aerially disseminated on the test grids, Test Area C-52A provided a 'field laboratory' for what may have happened in Vietnam, had there been no intercepting forest cover. However, in Vietnam a 'typical' mission would have disseminated 14.8 kg of 2,4,5-T/ha, most of which was intercepted by the forest canopy, versus the 876 kg 2,4,5-T/ha on the test grid at Eglin. Moreover, each hectare on the Eglin test grid received at least 1,300 times more TCDD than a hectare sprayed with Agent Orange in Vietnam. The disappearance or persistence of TCDD is dependent upon how it enters the ecosystem. Spray equipment test and evaluations missions at Eglin were generally scheduled and conducted with environmental conditions that were optimal for spray operations. This suggests that conditions favorable for dissemination of herbicide were the same conditions favorable for photodegradation of TCDD. It was likely that 99 percent of the TCDD never persisted beyond the day of application. No long-term adverse ecological effects were documented in these studies despite the massive quantities of herbicides and TCDD that were applied to the site. Reviews by the US Environmental Protection Agency and the National Academy of Sciences' Institute of Medicine did not address the fate of Agent Orange and TCDD as described in these studies from Eglin AFB, Florida.     

A survey of drinking water supplies in the Province of Ontario for dioxins and furans

A survey of drinking water supplies in the Province of Ontario was initiated in 1983 to determine the extent of their contamination by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). This drinking water survey arose from concerns regarding the discovery of PCDDs and PCDFs in sport fish from western Lake Ontario in the early 1980's.A total of 49 water supplies throughout all Regions of Ontario have been examined to date. Water supplies in the vicinity of chemical industries and pulp and paper mills were sampled more frequently; as many as 20 times. Detection limits were in the low parts per quadrillion (ppq) range for all tetra- to octachlorinated PCDDs and PCDFs.As of February 1989, 4, 347 results were received for 399 raw and treated water samples. Only 37 positive results were reported, constituting less than 1 percent of the total number of results. The O₈CDD congener accounted for 36 of the 37 positive results. The 2,3,7,8- TCDD isomer was not detected in any sample.     

Interactions of 2,2′,4,4′,5,5′-hexachlorobiphenyl and 2,3,7,8-tetrachlorodibenzo-p-dioxin in a subchronic feeding study in the rat

Female (SD) rats were fed diets containing 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB 153) in various concentrations for three months. PCB 153 had no significant effect on the body weight gain when given alone or in combination with TCDD. The increases in relative liver weights were additive. For thymic atrophy no interactive effects became apparent. PCB 153 had no effect on the EROD induction by TCDD. PROD induction by PCB 153 was diminished in the presence of TCDD. The level of TCDD in the liver was decreased by PCB 153. Increasing TCDD dosage led to an increase in PCB 153 levels.     

Gas chromatography/mass spectrometry applied for the analysis of triazine herbicides in environmental waters

The excess use of triazine herbicides in agriculture causes severe contamination to the environment especially for ground water. Gas chromatography coupled with mass spectrometry (GC/MS) was used to analyze simazine, atrazine (ATR), cyanazine, as well as the degradation products of ATR such as deethylatrazine and deisopropylatrazine in environmental water samples. These compounds were baseline separated by the established GC method. The water samples were pre-concentrated by solid-phase-extraction (SPE) and analyzed by ion trap MS at sub- to low-ppt levels. Recovery of ATR by the SPE pre-concentration using a C18 cartridge was determined as 90.5 +/- 3.5%. Detection limit of the method using selected ion monitoring technique for ATR was 1.7 ppt when one liter water was analyzed. The relative analytical error for ATR fortified water samples at 200 ppt was -12.5% (n=12) with triple analysis and the relative standard deviation was 3.2%. Trace levels of ATR at 3.9 and 9.7 ppt were determined in water samples collected from a reservoir and a river in Hong Kong.     

High-throughput screening of dioxins in sediment and soil using selective pressurized liquid extraction with immunochemical detection

A high-throughput screening method using selective pressurized liquid extraction (SPLE) and enzyme-linked immunosorbent assay (ELISA) for monitoring dioxins in sediment and soil is described. SPLE conditions were developed by extracting sediment or soil together with alumina, 10% AgNO₃ in silica, and sulfuric acid impregnated silica (acid silica) using dichloromethane (DCM) as the solvent at 100 °C and 2000 psi. Post-extraction cleanups were not required for ELISA. Two reference sediments (National Institute of Standards and Technology SRM 1944 and Wellington Laboratories WMS01) were analyzed by the SPLE–ELISA method. The ELISA utilized a polyclonal antibody and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as the calibrant. Recoveries of ELISA-derived TCDD equivalents (EQ) relative to the expected gas chromatography/high resolution mass spectrometry (GC/HRMS) derived dioxin toxic equivalent (TEQ) values were 116 ± 11% for SRM 1944 and 102 ± 13% for WMS01. ELISA TCDD EQs were consistent with the dioxin TEQs as measured by GC/HRMS for 25 soil/sediment samples from seven different contaminated sites. The ELISA had an approximate method detection limit of 10 pg g⁻¹ with a precision of 2.6–29% based on the relative percentage difference (%RPD) for duplicate samples. Estimated sample throughput for the SPLE–ELISA was three times or more than that of the GC/HRMS method employing PLE with a multi-column cleanup.     

Environmental fate and bioavailability of agent orange and its associated dioxin during the vietnam war

BACKGROUND: In 1996, the Committee on the Assessment of Wartime Exposure to Herbicides in Vietnam of the National Academy of Sciences' Institute of Medicine (IOM) issued a report on an exposure model for use in epidemiological studies of Vietnam veterans. This exposure model would consider troop locations based on military records; aerial spray mission data; estimated ground spraying activity; estimated exposure opportunity factors; military indications for herbicide use; and considerations of the composition and environmental fate of herbicides, including changes in the TCDD content of the herbicides over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of the herbicides into the ground. When the final report of the IOM Committee was released in October 2003, several components of the exposure model envisioned by the Committee were not addressed. These components included the environmental fate of the herbicides, including changes in the TCDD content over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of herbicides into the ground. This paper is intended to help investigators understand better the fate and transport of herbicides and TCDD from spray missions, particularly in performing epidemiological studies. METHODS: This paper reviews the published scientific literature related to the environmental fate of Agent Orange and the contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), and discusses how this affected the potential exposure to TCDD of ground troops in Vietnam. Specifically, the mechanisms of dissipation and degradation as they relate to environmental distribution and bioavailability are addressed. RESULTS: The evaluation of the spray systems used to disseminate herbicides in Vietnam showed that they were capable of highly precise applications both in terms of concentrations sprayed and area treated. Research on tropical forest canopies with leaf area indices (a measure of foliage density) from 2 to 5 indicated that the amount of herbicide and associated TCDD reaching the forest floor would have been between 1 and 6% of the total aerial spray. Studies of the properties of plant surface waxes of the cuticle layer suggested that Agent Orange, including the TCDD, would have dried (i.e., be absorbed into the wax layer of the plant cuticle) upon spraying within minutes and could not be physically dislodged. Studies of Agent Orange and the associated TCDD on both leaf and soil surface have demonstrated that photolysis by sunlight would have rapidly decreased the concentration of TCDD, and this process continued in shade. Studies of 'dislodgeable foliar residues' (DFR, the fraction of a substance that is available for cutaneous uptake from the plant leaves) showed that only 8% of the DFR was present 1 hr after application. This dropped to 1% of the total 24 hrs after application. Studies with human volunteers confirmed that after 2 hrs of saturated contact with bare skin, only 0.15-0.46% of 2,4,5-T, one of the phenoxy acetic acid compounds that was an active ingredient of Agent Orange, entered the body and was eliminated in the urine. CONCLUSIONS: The prospect of exposure to TCDD from Agent Orange in ground troops in Vietnam seems unlikely in light of the environmental dissipation of TCDD, little bioavailability, and the properties of the herbicides and circumstances of application that occurred. Photochemical degradation of TCDD and limited bioavailability of any residual TCDD present in soil or on vegetation suggest that dioxin concentrations in ground troops who served in Vietnam would have been small and indistinguishable from background levels even if they had been in recently treated areas. Laboratory and field data reported in the literature provide compelling evidence on the fate and dislodgeability of herbicide and TCDD in the environment. This evidence of the environmental fate and poor bioavailability of TCDD from Agent Orange is consistent with the observation of little or no exposure in the veterans who served in Vietnam. Appreciable accumulation of TCDD in veterans would have required repeated long-term direct skin contact of the type experienced by United States (US) Air Force RANCH HAND and US Army Chemical Corps personnel who handled or otherwise had direct contact with liquid herbicide, not from incidental exposure under field conditions where Agent Orange had been sprayed.     

In vitro assessment of AhR-mediated activities of TCDD in mixture with humic substances

Humic substances (HS) are ubiquitous natural products of decomposition of dead organic matter. HS is present in most freshwaters at concentrations ranging from 0.5 to 50 mg L⁻¹. Organic carbon can represent 20% dry weight of sediments. Recently, the interaction of dissolved HS with the aryl hydrocarbon receptor (AhR) has been demonstrated. The AhR is a cytosolic receptor to which persistent organic pollutants (POPs) can bind and many of their toxic effects are mediated through interactions with this receptor. We describe in vitro effects (using H4IIE-luc cells) of binary mixtures of various HS with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), since in contaminated environments these compounds occur simultaneously. Six out of 12 HS samples activated AhR even at environmentally relevant concentrations (17 mg L⁻¹), but did not reach the full AhR-activation even at excessive concentration. In simultaneous exposure of H4IIE-luc to HS (17 mg L⁻¹) and TCDD (1.2 pM) without any preincubation prior to exposure, either significant additive or facilitative effects were observed. No negative interactions, due to possible sorption of TCDD to HS was observed. Nevertheless, if the HS–TCDD binary mixture was preincubated for 6 days prior to the exposure on H4IIE-luc cells, the additive and facilitative effects were less due to possible sorption of TCDD onto HS. Similar results were obtained from analogous experiments with greater concentrations of both TCDD and HS.