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.     

Catalytic NO(chi) reduction with simultaneous dioxin and furan oxidation

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NO(chi)- and CO-emissions are reduced by 90% and 20% to about 50 mg/N m3 andbelow 10 mg/N m3, respectively.     

Uptake and accumulation of mercury from dental amalgam in the common goldfish,Carassius auratus

In this study, the bioavailability and accumulation of mercury from external environmental exposure to mixed, cured, milled, sieved and proportioned dental amalgam was examined in the common goldfish, Carassius auratus. Fish were exposed to dental amalgam (particle size range from < 0.10 to 3.15 mm) in order to represent the particle size and distribution of that found within the typical dental office wastewater discharge stream. Experimental amalgam water loadings were 0 g/l, 0.5 g/l and 1 g/l in glass aquaria at 15 degrees C for 28 days. Fish tissues were sampled at 5 min and 28 days of exposure, and the liver, brain, muscle and whole body analyzed for total mercury using cold vapor atomic fluorescence spectroscopy. Mercury was found in several tissues examined and generally increased with exposure to higher amounts of dental amalgam. The highest levels were found in the whole body (17.68 +/- 5.73 microg/g) followed by the liver (0.80 +/- 0.16 microg/g) and muscle (0.47 +/- 0.16 microg/g). The lowest concentrations were seen in the brain (0.28 +/- 0.19 microg/g). Compared to controls, concentrations in the whole body, muscle and liver in fish exposed for 28 days to the highest concentration of amalgam were 200-, 233-, and 40-fold higher, respectively. This study shows that mercury from an environmental exposure to representative samples of dental amalgam typically found within the dental wastewater discharge stream is bioavailable to fish and may accumulate in internal tissues.     

Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

Predicting invasion risk using measures of introduction effort and environmental niche models.

The Chinese mitten crab (Eriocheir sinensis) is native to east Asia, is established throughout Europe, and is introduced but geographically restricted in North America. We developed and compared two separate environmental niche models using genetic algorithm for rule set prediction (GARP) and mitten crab occurrences in Asia and Europe to predict the species' potential distribution in North America. Since mitten crabs must reproduce in water with >15% per hundred salinity, we limited the potential North American range to freshwater habitats within the highest documented dispersal distance (1260 km) and a more restricted dispersal limit (354 km) from the sea. Applying the higher dispersal distance, both models predicted the lower Great Lakes, most of the eastern seaboard, the Gulf of Mexico and southern extent of the Mississippi River watershed, and the Pacific northwest as suitable environment for mitten crabs, but environmental match for southern states (below 35 degrees N) was much lower for the European model. Use of the lower range with both models reduced the expected range, especially in the Great Lakes, Mississippi drainage, and inland areas of the Pacific Northwest. To estimate the risk of introduction of mitten crabs, the amount of reported ballast water discharge into major United States ports from regions in Asia and Europe with established mitten crab populations was used as an index of introduction effort. Relative risk of invasion was estimated based on a combination of environmental match and volume of unexchanged ballast water received (July 1999-December 2003) for major ports. The ports of Norfolk and Baltimore were most vulnerable to invasion and establishment, making Chesapeake Bay the most likely location to be invaded by mitten crabs in the United States. The next highest risk was predicted for Portland, Oregon. Interestingly, the port of Los Angeles/Long Beach, which has a large shipping volume, had a low risk of invasion. Ports such as Jacksonville, Florida, had a medium risk owing to small shipping volume but high environmental match. This study illustrates that the combination of environmental niche- and vector-based models can provide managers with more precise estimates of invasion risk than can either of these approaches alone.     

Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium

Levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and polychlorinated biphenyls (PCBs) were measured in several fish species originating from the river Scheldt (Belgium). Five sampling locations were chosen in a highly industrialized area along the river, while two ponds in the vicinity of the river served as reference sites. The present study is a follow-up of a survey performed in 2000 which reported extremely high levels of PBDEs and HBCDs in eel (Anguilla anguilla) collected from the same region (Oudenaarde, Flanders). The sum of tri- to hepta-BDE congeners (2270+/-2260 ng/g lipid weight (lw), range 660-11500 ng/g lw) and total HBCDs (4500+/-3000 ng/g lw, range 390-12100 ng/g lw) were one order of magnitude higher than levels usually reported from freshwater systems, indicating the presence of point sources. In most samples, levels of total HBCDs were higher than those of PBDEs, probably due to the high density of factories using HBCD as an additive brominated flame retardant (BFR). The high values of HBCDs were confirmed by both gas- and liquid-chromatography-mass spectrometry. Although BFR levels were between the highest ever reported in freshwater ecosystems, PCBs could be detected at even higher concentrations (16000+/-14300 ng/g lw, range 3900-66600 ng/g lw), being among the highest levels recorded in Belgium. The inter-sampling site variation of PBDEs, HBCDs and PCBs was comparable. All locations presented similar PBDE congener profiles, with BDE 47 being the dominant congener, followed by BDE 100, BDE 99 and BDE 49, probably originating from the former use of the penta-BDE technical mixture. In order to estimate the impact of these point sources on human exposure, we further focussed on eels which showed a considerable decrease in the PBDE and HBCD levels between 2000 and 2006. Due to the wide span in concentrations between the different sampling locations, a variable contribution to the total human exposure through local eel consumption was estimated. The calculated daily intake ranged from 3 ng to 330 ng PBDEs/day for normal eel consumers, but was as high as 9800 ng PBDEs/day for anglers, which may be considered at risk.     

The United States Department of Energy's Regional Carbon Sequestration Partnerships Program Validation Phase

This paper reviews the Validation Phase (Phase II) of the Department of Energy's Regional Carbon Sequestration Partnerships initiative. In 2003, the U.S. Department of Energy created a nationwide network of seven Regional Carbon Sequestration Partnerships (RCSP) to help determine and implement the technology, infrastructure, and regulations most appropriate to promote carbon sequestration in different regions of the nation. The objectives of the Characterization Phase (Phase I) were to characterize the geologic and terrestrial opportunities for carbon sequestration; to identify CO(2) point sources within the territories of the individual partnerships; to assess the transportation infrastructure needed for future deployment; to evaluate CO(2) capture technologies for existing and future power plants; and to identify the most promising sequestration opportunities that would need to be validated through a series of field projects. The Characterization Phase was highly successful, with the following achievements: established a national network of companies and professionals working to support sequestration deployment; created regional and national carbon sequestration atlases for the United States and portions of Canada; evaluated available and developing technologies for the capture of CO(2) from point sources; developed an improved understanding of the permitting requirements that future sequestration activities will need to address as well as defined the gap in permitting requirements for large scale deployment of these technologies; created a raised awareness of, and support for, carbon sequestration as a greenhouse gas (GHG) mitigation option, both within industry and among the general public; identified the most promising carbon sequestration opportunities for future field tests; and established protocols for project implementation, accounting, and management. Economic evaluation was started and is continuing and will be a factor in project selection. During the Validation Phase, the seven regional partnerships will put the knowledge learned during the Characterization Phase into practice through field tests that will validate carbon sequestration technologies that are best suited to their respective regions of the country. These tests will verify technologies developed through DOE's core R&D effort and enable implementation of CO(2) sequestration on a large scale, should that become necessary. Pilot projects will have a site-specific focus to test technology; assess formation storage capacity and injectivity; validate and refine existing CO(2) formation models used to determine the transport and fate of CO(2) in the formation; demonstrate the integrity of geologic seals to contain CO(2); validate monitoring, mitigation, and verification (MMV) technologies; define project costs and compare costs of alternatives; assess potential operational and long-term storage risks; address regulatory requirements; and engage and evaluate public acceptance of sequestration technologies. Field validation tests involving both sequestration in geologic formations and terrestrial sequestration are being developed. The results from the Validation Phase will help to confirm the estimates made during the Characterization Phase and will be used to update the regional atlases and NatCarb. Answers to many questions about the effectiveness and safety of carbon sequestration technologies will be instrumental in planning for a Deployment Phase, in which large volume tests will be planned to further sequestration as an option that can mitigate GHG emissions in the United States.     

Perfluorooctane sulfonic acid and organohalogen pollutants in liver of three freshwater fish species in Flanders (Belgium): relationships with biochemical and organismal effects

A perfluorooctane sulfonic acid (PFOS) assessment was conducted on gibel carp (Carassius auratus gibelio), carp (Cyprinus carpio), and eel (Anguilla anguilla) in Flanders (Belgium). The liver PFOS concentrations in fish from the Ieperlee canal (Boezinge, 250-9031 ng/g wet weight, respectively) and the Blokkersdijk pond (Antwerp, 633-1822 ng/g wet weight) were higher than at the Zuun basin (Sint-Pieters-Leeuw, 11.2-162 ng/g wet weight) and among the highest in feral fish worldwide. Eel from the Oude Maas pond (Dilsen-Stokkem) and Watersportbaan basin (Ghent) had PFOS concentrations ranging between 212 and 857 ng/g wet weight. The hepatic PFOS concentration was significantly and positively related with the serum alanine aminotransferase activity, and negatively with the serum protein content in eel and carp. The hepatic PFOS concentration in carp correlated significantly and negatively with the serum electrolyte concentrations whereas a significant positive relation was found with the hematocrit in eel. Although 13 organochlorine pesticides, 22 polychlorinated biphenyl (PCB) congeners and 7 polybrominated diphenyl ethers (PBDEs) were also measured in the liver tissue, only PCB 28, PCB 74, gamma-hexachlorocyclohexane (gamma-HCH) and hexachlorobenzene (HCB) were suggested to contribute to the observed serological alterations in eel.     

Country report: Broiler industry and broiler litter-related problems in the southeastern United States

This report describes the development of the broiler litter problem in the southeastern United States, including the economic opportunity and environmental challenges brought to the region by the industry. Through an analysis applied to the State of Georgia, land application of litter as a disposal alternative is examined along with its associated benefits. The analysis indicates that litter could be transported economically up to 256 km for cropland application. Excessive broiler litter production in a few concentrated regions is expected to stimulate the development of alternative approaches to broiler litter management, such as electricity generation.     

Preliminary Studies on Converting Agricultural Waste into Biodegradable Plastics – Part III: Sawdust

Summary Hardwood sawdust was derivatized either by carboxymethylation, glutaration, maleiation, phthallation, or succination in order to produce anionic materials suitable for complexation with soy protein isolate. Blending each derivative with soy protein isolate resulted in instant precipitation of gels. Infrared spectroscopy and differential scanning calorimetry suggested that each derivative formed a complex with protein. Reaction products could be dried into pellets exhibiting tensile strengths between 0.9–2.4 MPa, suggested that these materials could be promising candidates for biodegradable structural materials.