Ozone treatment of soil contaminated with aniline and trifluralin

Column studies were conducted to determine the ability of ozone to degrade aniline and trifluralin in soil. Ozone rapidly degraded aniline from soil under moist soil conditions, 5% (wt). Removal of 77-98% of [UL-14C]-aniline was observed from soil columns (15 ml, i.d. = 2.5 cm), exposed to 0.6% O(3) (wt) at 200 ml/min after 4 min. Initial ozonation products included nitrosobenzene and nitrobenzene, while further oxidation led to CO(2). Ring-labeled-[UL-14C]-trifluralin removal rates were slower, requiring 30 min to achieve removals of 70-97%. Oxidation and cleavage of the N-propyl groups of trifluralin was observed, affording 2,6-dinitro-4-(trifluoromethyl)-aniline, 2,6-dinitro-N-propyl-4-(trifluoromethyl)-benzamine, and 2,6-dinitro-N-propyl-N-acetonyl-4-(trifluoromethyl)-benzamine. Base solutions revealed that trifluralin was similarly oxidized to CO(2), where 72-83% of the activity recovered comprised 14CO(2). Use of ozone-rich water improved contaminant removal in trifluralin-amended soil columns, but did not improve removal in aniline, pentachloroaniline, hexachlorobenzene amended soil columns, suggesting that ozonated water may improve contaminant removal for reactive contaminants of low solubility.     

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.     

Trends in organochlorine and mercury levels in Gannet eggs

Levels of DDE, HEOD, PCBs and mercury were measured in Gannet eggs from several colonies around Britain during 1971-1987. At two colonies (Ailsa Craig and Bass Rock) sampled throughout this period, organochlorine levels declined between the early 1970s and 1983, and then increased again. The trends at other colonies, sampled over shorter periods, were generally consistent with those at Ailsa Craig and Bass Rock. Trends in mercury levels were more variable, and increases were observed at four colonies and declines at two. Some shell-thinning occurred in association with DDE contamination. However, levels of this chemical were too low to affect breeding success in the years concerned. The same was probably true of the other chemicals.     

Long-term trends in organochlorine and mercury residues in some predatory birds in Britain

Residue levels of organochlorine pesticides (HEOD, DDE), polychlorinated biphenyls (PCBs) and mercury (Hg) in the livers of five predatory bird species were monitored in Britain over a 28-year (1963-1990) period. Of two raptor species, sparrowhawks contained higher levels of most chemicals than did kestrels. Among three fish-eaters, herons and kingfishers contained the highest levels of DDE and HEOD, while herons and great-crested grebes contained the highest levels of PCBs and mercury. Species differences were related partly to diet and habitat. In sparrowhawks and kestrels, residues of HEOD and DDE were higher in eastern, arable districts than elsewhere, especially in the 1960s and 1970s. In the fish-eaters, similar regional differences in residue levels were apparent in herons, especially in the 1970s, but not in the other species, for which samples were smaller. Over the 28 years, most species showed significant downward trends in HEOD, DDE and Hg levels, but only two fish-eaters showed significant declines in PCB levels. The downward trends in DDE and HEOD followed successive restrictions in the use of organochlorine pesticides, and were accompanied by recoveries in the populations and breeding success of affected species. Downward trends in mercury were associated with reductions in both agricultural use and industrial emissions.     

Uptake of cadmium in tropical marine lamellibranchs,and effects on physiological behaviour

The effect of cadmium introduced as inorganic salts (chloride, nitrate, sulfate, carbonate, acetate and iodide) or organic chelates (with EDTA, NTA and humic acid) on the physiological behaviour of six species of tropical lamellibranchs — arcid blood clamsAnadara granosa andA. rhombea, venerid clamsMeretrix casta andKatelysia opima, and mytilid musselsPerna viridis andP. indica, collected from various intertidal areas in southern India from 1986 to 1989 — was evaluated. Inorganic salts of Cd are reported to completely ionize upon introduction to full-strength sea water and form predominantly (97%) chloride complexes. Some inorganic Cd salts, therefore, would hardly affect physiological parameters. However, bioaccumulation of Cd was greatest upon exposure to Cd introduced as sulfate, followed by iodide, acetate, chloride, nitrate and carbonate; 96-h LC₅₀'s also varied, but in a different order, being highest for chloride (3.5µg ml^–1), followed by nitrate, acetate, iodide and sulfate (1.8µg ml^–1). Furthermore, Cd levels increased linearly with time of exposure and levels in medium, and were species-specific, being highest in the arcid clams, followed by the venerid clams and mytilid mussels. The presence of other metals such as Zn reduced bioaccumulation of Cd significantly (P < 0.001), but the reverse was not true. Upon exposure to Cd in the presence of Cu, on the other hand, accumulation of both metals was reduced by 15 to 20%. In the presence of organic chelators — EDTA, NTA and reduced glutathione (GSH) — Cd accumulation was significantly inhibited, by 1/2 to 1/3. Humic acid, on the other hand, had no effect. Cd levels in soft tissues were inversely related to ambient salinity in the range of 12 to 32. However, both Zn and Cu significantly inhibited Cd accumulation irrespective of salinity. Cd increased the rate of filtration inAnadara granosa over the first 24 h by 28%, but on prolonged exposure (96 h) that rate decreased significantly, by 50%. Zn alone and in the presence of Cd, on the contrary, initially reduced filtration activity, which subsequently increased to control levels upon continued exposure. Cu alone and in combination with Cd and Zn also significantly (P < 0.001) inhibited filtration relative to controls. This combination also progressively reduced respiratory activity with time, the maximum decrease being 80% after 96 h of exposure. Furthermore, impact of all three metals on both filtration rate and oxygen consumption was initially synergistic, but changed to antagonistic upon prolonged exposure up to 96 h.Deceased. Please send all correspondence and requests for reprints to Dr. S. Patel at the same address     

Growth response of loblolly pine (Pinus taeda L.) seedlings to ozone fumigation

Twenty-two week-old Pinus taeda L. (loblolly pine) seedlings of 30 open-pollinated and five full-sib families, representing a wide range in geographic origin, were grown in charcoal-filtered (CF) air or CF-air supplemented with 160 or 320 nl liter(-1) ozone for 8 h day(-1), 4 days week(-1), for 9 weeks. Visible foliar injury (banded chlorosis, tip burn and premature senescence) was apparent in many families after 3 weeks in 320 nl liter(-1) and 6 weeks in 160 nl liter(-1) ozone. Decreases in relative height and root collar diameter growth rates, total dry weight, root dry weight, shoot dry weight, and root/shoot ratios were evident after 9 weeks of treatment with both 160 and 320 nl liter(-1) ozone. For relative height growth rates, family differences in response to ozone were observed. By the study's end, net photosynthesis rates were 15% less for the 320 nl liter(-1) ozone treatment as compared to the CF-air treatment. Total soluble sugar and total starch content of roots were not changed after 9 weeks of ozone exposure.     

Controls on leaching of N species in upland moorland catchments

Spatial and temporal changes in mobility of N species have been studied for three UK upland river networks, the Etherow in the South Pennines, the Nether Beck in the Lake District and the Dee in NE Scotland. The catchments are subject to N deposition at 35.1, 22.0 and 10.8–15.6 kg N ha^?1 yr^?1, respectively. The NH⁺ ₄ leaching appears to be predominantly regulated by flow path in more polluted upland catchments. It is greatest where water draining acidified peaty soils contributes more to total discharge. Soluble organic matter may provide the dominant counter anion. In the Etherow and Dee catchments, which are dominated by acid mineral and organic soils, at high discharge NO^? ₃ also appears to be associated with greater input of water from acidified soils. In contrast, for the Nether Beck, higher NO^? ₃ concentrations are associated with tributaries draining soils contributing water with higher alkalinity, suggesting nitrification is important. For the Etherow and Dee, dissolved organic N (DON) appears to originate predominantly from acidified, peaty soils. Spiking experiments with peat soil from the Etherow catchment confirmed the limited capacity of these soils to utilize inorganic N inputs, favouring equilibration with NH⁺ ₄ inputs and leaching losses of inorganic N throughout the year.     

The Application of the Ecological Footprint: a case of passenger transport in Merseyside

The release of carbon dioxide from the burning of fossil fuels is believed to be responsible for climate change. In the UK, road transport emits 22% of the total output of carbon dioxide. This study applies the ecological footprint to Merseyside to ascertain the global environmental impact of passenger transport (expressed in hectares). Results show that car travel has a footprint of 704 000 hectares, which is 87% of the total footprint. It is demonstrated in scenarios that Policy initiatives involving the Local Transport Plan will cause the footprint to increase. It is also shown that individual behaviour could be influenced when highlighting the impacts of different modes of transport along the same route. By using the ecological footprint in educational programmes, the effect can be shown of carbon emissions and land appropriation on the 'school run'; these issues could be promoted alongside others such as health, safety, congestion, global equity and fairness.     

AN INTEGRATIVE APPROACH TOWARDS UNDERSTANDING ECOLOGICAL RESPONSES TO DAM REMOVAL: THE MANATAWNY CREEK STUDY1

ABSTRACT: Dam removal has been proposed as an effective method of river restoration, but few integrative studies have examined ecological responses to the removal of dams. In 1999, we initiated an interdisciplinary study to determine ecological responses to the removal of a 2 m high dam on lower Manatawny Creek in southeastern Pennsylvania. We used an integrative monitoring program to assess the physical, chemical, and biological responses to dam removal. Following removal in 2000, increased sediment transport has led to major changes in channel form in the former impoundment and downstream reaches. Water quality did not change markedly following removal, probably because of the impoundment's short hydraulic residence time (less than two hours at base flow) and infrequent temperature stratification. When the impoundment was converted to a free flowing reach, the composition of the benthic macroinvertebrate and fish assemblages in this portion of Manatawny Creek shifted dramatically from lentic to lotic taxa. Some fish species inhabiting the free flowing reach downstream from the dam were negatively affected by large scale sediment transport and habitat alteration following dam removal, but this appears to be a short term response. Based on our observations and experiences in this study, we provide a list of issues to evaluate when considering future dam removals.     

Sustainable public/private partnerships for public service delivery

This article defines three kinds of public/private partnership, lists their potential benefits and explains common issues and problems in their operation with examples from developing countries. It then defines and discusses the concepts of social sustainability and financial sustainability in relation to public/private partnerships, and emphasizes the importance of applying sustainability criteria to each partner. It is argued that essentially the same criteria apply to non-profit NGOs as to for-profit firms, despite their differences in goals and values. The article concludes with some suggested strategies for effective international technical co-operation in the establishment of public/private partnerships.