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.     

Bioremediation of coal tar PAH in soils using biodiesel

The addition of biodiesel together with nitrate and phosphate to soil containing coal tar, in laboratory and field experiments, resulted in degradation of coal tar polycyclic aromatic hydrocarbons (PAH) that was not apparent when the nutrients alone were added. The addition of motor diesel fuel instead of biodiesel was also tested. Over the 55 days of the field and laboratory experiments, the biodiesel resulted in an increased degradation of naphthalene in the coal tar by 52% and 85%, respectively, and motor diesel resulted in increased depletions of 85% and 96%, respectively. Other PAH containing up to four rings were depleted to lesser extents. The increases in PAH biodegradation by the diesel treatments were ascribed to tar solubilisation and dispersion thereby increasing the PAH bioavailability. The ready biodegradability and low phytotoxicity of biodiesel suggest that it may be suitable as a novel treatment for the bioremediation of coal tar contaminated soils.     

Assessment of natural components of PM10 at UK urban and rural sites

Proposals from the European Commission have raised the possibility that Member States may be able to subtract the concentrations of natural components of airborne particulate matter from measured concentrations when evaluating compliance with EU Limit Values. By applying the pragmatic mass closure model [Harrison et al., 2003. A pragmatic mass closure model for airborne particulate matter at urban background and roadside sites. Atmospheric Environment 37, 4927–4933] to chemical composition data for PM₁₀, it has been possible to estimate the concentrations of natural sea salt, strongly bound water and secondary organic carbon (which is assumed wholly biogenic) to the measured mass of PM₁₀. Because of the difficulty in distinguishing between natural and anthropogenic crustal dusts, the contribution of natural windblown dust and soil has not been accounted for. When the natural components are estimated for two urban and one rural site in the UK, the long-term mean PM₁₀ concentration is reduced by between 5.2 and 7.3 μg m⁻³. The number of exceedences of the 50 μg m⁻³ 24-h limit value falls dramatically from 54 to 21 (from a total of 291 days) at an urban street canyon site, 7 to 3 (n=292 days) at an urban background site and from 8 to 0 (n=241 days) at a rural site when using gravimetric PM₁₀ concentrations. The calculations have also been performed using PM₁₀ concentrations measured by TEOM increased by a factor of 1.3 as recommended by the European Commission as an interim means of estimating gravimetric equivalency, and the number of exceedences of the 24-h limit value fell from 92 to 47 (from a total of 291 days) at the urban street canyon site, from 11 to 3 (n=292 days) at the urban background site and from 6 to 3 (n=241) at the rural site. Clearly, therefore, application of this proposed measure would make a very major difference to the likelihood of compliance or otherwise with the 24-h limit value for PM₁₀.     

Foliar leaching of 137Cs from Eriophorum vaginatum L., Scirpus caespitosus L. and Erica tetralix L

Evidence of extensive leaching losses of nutrients, particularly of K, suggest that loss of 137Cs by foliar leaching could be considerable and could stimulate further root uptake and redistribution of 137Cs in plants. This study investigated the foliar leaching of 137Cs from two deciduous graminoid species, Eriophorum vaginatum and Scirpus caespitosus and one evergreen shrub, Erica tetralix. Plants were labelled with 137Cs via the roots and subjected to a leaching treatment in August and November and changes in both leachate and plant 137Cs activity were determined. Leaching losses were significantly reduced in November compared with August in the deciduous species, but not in the evergreen E. tetralix. A reduction in the total activity of 137Cs of leached plants was observed not only in leaves but also in stems and roots in some instances, suggesting that 137Cs from these organs had been redistributed to replenish that lost by leaching from the leaves. The data suggest that leaching losses were greater from older and senescent leaves than from younger leaves of E. vaginatum. The extent to which this is an accurate representation of foliar leaching of field-grown plants by rainfall, and the likely fate of 137Cs lost by foliar leaching are discussed.     

Assessment of organic contaminant fate in waste water treatment plants. I: Selected compounds and physicochemical properties

An extensive and comprehensive literature review has been conducted for compounds which we hypothesise could be present in sludge and maintain their integrity following application to agricultural land. The following compounds have been selected for review; chlorinated paraffins, quintozene, brominated diphenyl ethers, polychlorinated naphthalenes, polydimethylsiloxanes, chloronitrobenzenes, and a range of biologically active and pharmaceutical compounds. All have received interest as a result of their persistence and/or toxicity in environmental media. Physicochemical property information has also been compiled and/or calculated. In this way, an accompanying paper will attempt to predict compound fate in waste water treatment plants (WWTPs) and assess likely transfers from soil/plants to grazing livestock. These papers describe a first attempt to predict the fate of these classes of compounds in the environment and prioritise those of greatest concern.     

An assessment of the sensitivity and reliability of the relative reduction factor approach in the development of 8-hr ozone attainment plans

The updated regulatory framework for demonstrating that future 8-hr ozone (O3) design values will be at or below the National Ambient Air Quality Standards (NAAQS) provides guidelines for the development of a State Implementation Plan (SIP) that includes methods based on photochemical modeling and analytical techniques. One of the suggested approaches is the relative reduction factor (RRF) for estimating the efficacy of emission reductions. In this study, the sensitivity of model-predicted responses towards emission reductions to the choice of meteorology and chemical mechanisms was examined. While the different modeling simulations generally were found to be in agreement on whether predicted future-year design values would be above or below the NAAQS for 8-hr O3 at a majority of the monitoring locations in the eastern United States, differences existed for a small percentage of monitors (approximately 6.4%). Another issue investigated was the ability of the attainment demonstration procedure to predict changes in monitored O3 design values. A retrospective analysis was performed by comparing predicted O3 design values from model simulations using emission estimates for 1996 and 2001 with monitored O3 design values for 2001. Results indicated that an average gross error of approximately 5 ppb was present between modeled and observed design values and that, at approximately 27% of all sites, model-predicted and observed design values disagreed as to whether the design value was above or below the NAAQS. Retrospective analyses such as the one presented in this study can provide valuable insights into the strengths and limitations of modeling and analysis techniques used to predict future design values over time periods of a decade or more for the purpose of developing SIPs. Furthermore, such analyses could provide avenues for improvement and added confidence in the use of the RRF approach for addressing attainment of the NAAQS.     

The effect of heavy metals on dinitrogen fixation by Rhizobium-white clover in a range of long-term sewage sludge amended and metal-contaminated soils

An investigation was conducted to determine whether effective strains of Rhizobium leguminosarum biovar. trifolii capable of symbiotic N2 fixation with white clover (Trifolium repens) were present in a range of metal-contaminated soils. A number of historically sewage-amended sites (including experimental, pasture grassland and arable sites) were selected and compared with highly contaminated samples from abandoned heavy metal mines. Many sites had metal concentrations above the limits established by the UK Government, based on those developed by the European Commission (EC) for sludge-amended soils. Acetylene reduction activity (ARA) was used to screen the samples for effective N2 fixation. When the host plant was indigenous to the sward, rhizobia were found in the nodules and in the soil rhizosphere at all the sites tested. They were shown to be capable of effective symbiosis and N2 fixation, even though metal concentrations greatly exceeded the soil metal limits in some cases. However, nodulation failed to occur in some cases where T. repens was not indigenous to metal-contaminated soils. This indicated either that an ineffective rhizobial population was present, or that effective cells were absent from the soil. The influence of individual metals on ARA could not be determined conclusively because of the confounding effects of soil physicochemical variability and the presence of different metals at high concentrations together in the soil. However, Cd concentrations appeared to be particularly important in determining the presence of effective ARA in soils with no indigenous clover. In contrast to previous studies, the results presented here suggest that heavy metals may have had a quantitative effect on the free-living population of rhizobia, rather than a genetic effect.     

A field study of the generation of nitrate in a hill cap cloud

A field experiment to investigate the formation of nitrate as an airstream passes through a hill cap cloud has been performed at the UMIST field station on Great Dun Fell. It has been shown that the aerosol nitrate concentration increased by about 0.5 microg m(-3) as the airstream passed through the cloud during the night. At sunrise the nitrate production disappeared. It is suggested that the most likely mechanism for this nitrate production was due to the solution of N2O5 and NO3 formed from the reaction of NO2 with O3. These higher oxides build up overnight in the absence of short wave radiation to photolyse them. Other possible mechanisms of nitrate production are also discussed.     

The microbial role in hot spring silicification

Recent experimental studies indicate that microorganisms play a passive role in silicification. The organic functional groups that comprise the outer cell surfaces simply serve as heterogeneous nucleation sites for the adsorption of polymeric and/or colloidal silica, and because different microorganisms have different cell ultrastructural chemistry, species-specific patterns of silicification arise. Despite their templating role, they do not appear to increase the kinetics of silicification, and at the very most, they contribute only marginally to the magnitude of silicification. Instead, silicification is due to the polymerization of silica-supersaturated hydrothermal fluids upon discharge at the surface of the hot spring. Microorganisms do, however, impart an influence on the fabric of the siliceous sinters that form around hot spring vents. Different microorganisms have different growth patterns, that in turn, affect the style of laminations, the primary porosity of the sinter and the distribution of later-stage diagenetic cementation.     

Die Aleuronzellen des keimenden Getreides

Während der Vorbereitungen zu diesem Artikel war R. L. J. als Preisträger der Alexander-von-Humboldt-Stiftung in Göttingen tätig. Unsere Forschung auf diesem Gebiet wurde durch großzügige Hilfe der Deutschen Forschungsgemeinschaft und der National Science Foundation (USA) ermöglicht. Außerdem sind wir B. Raufeisen für die Herstellung der Zeichnungen sehr zu Dank verpflichtet.