Atmospheric lead deposition to Okefenokee Swamp, Georgia, USA

Contamination of the environment from atmospheric deposition during the twentieth century is pervasive even in areas ostensibly considered pristine or remote from point sources. In this study, Pb concentrations in a 210Pb-dated peat core collected from the Okefenokee Swamp, GA were used to assess historical contaminant input via atmospheric deposition. Lead isotope ratios were determined by dynamic reaction cell ICP-MS (DRC-ICP-MS). Increases in Pb concentration occurred in the late nineteenth century and a marked rise in Pb concentrations pre-dated the widespread use of leaded gasoline within the US. The 206Pb/207Pb ratios of 1.19 during this period were consistent with coal combustion emissions. A later increase in Pb concentration, concurrent with a trend toward more radiogenic 206Pb/207Pb ratios in gasoline is consistent with an increased input of Pb from leaded gasoline emissions. However, it appears that coal combustion emissions remain a major source of Pb to the Okefenokee.     

The effect of ozone on pollen development in Lolium perenne L

Perennial ryegrass plants (Lolium perenne L.) were exposed in "Closed-Top Chambers" to different ozone concentrations and to charcoal filtered ambient air to study the effect of ozone on the development of pollen. Ozone at ambient (65 nl l(-1), 8h) and elevated (110 nl l(-1), 4h) concentrations affected the maturing of pollen by inhibiting starch accumulation in pollen throughout the anther. Affected pollen persisted in the vacuolated state while normal pollen in the same anther were filled with amyloplasts. The percentage of underdeveloped pollen-determined in transversal sections-was significantly higher in exposed plants than in plants grown in filtered air. Results indicate that ozone stress was responsible for the disrupted development of pollen in L. perenne.     

The effect of EDTA and citric acid on phytoremediation of Cd, Cr, and Ni from soil using Helianthus annuus

The possibility to clean heavy metal contaminated soils with hyperaccumulator plants has shown great potential. One of the most recently studied species used in phytoremediation applications are sunflowers. In this study, two cultivars of Helianthus annuus were used in conjunction with ethylene diamine tetracetic acid (EDTA) and citric acid (CA) as chelators. Two different concentrations of the chelators were studied for enhancing the uptake and translocation of Cd, Cr, and Ni from a silty-clay loam soil. When 1.0 g/kg CA was used, the highest total metal uptake was only 0.65 mg. Increasing the CA concentration posed a severe phytotoxicity to both cultivars as evidenced by stunted growth and diminished uptake rates. Decreasing the CA concentration to 0.1 and 0.3 g/kg yielded results that were not statistically different from the control. EDTA at a concentration of 0.1 g/kg yielded the best results for both cultivars achieving a total metal uptake of approximately 0.73 mg compared to approximately 0.40 mg when EDTA was present at 0.3 g/kg.     

Preliminary ecotoxicological characterization of a new energetic substance, CL-20

A new energetic substance hexanitrohexaazaisowurtzitane (or CL-20) was tested for its toxicities to various ecological receptors. CL-20 (epsilon-polymorph) was amended to soil or deionized water to construct concentration gradients. Results of Microtox (15-min contact) and 96-h algae growth inhibition tests indicate that CL-20 showed no adverse effects on the bioluminescence of marine bacteria Vibrio fischeri and the cell density of freshwater green algae Selenastrum capricornutum respectively, up to its water solubility (ca. 3.6 mg l(-1)). CL-20 and its possible biotransformation products did not inhibit seed germination and early seedling (16-19 d) growth of alfalfa (Medicago sativa) and perennial ryegrass (Lolium perenne) up to 10,000 mg kg(-1) in a Sassafras sandy loam soil (SSL). Indigenous soil microorganisms in SSL and a garden soil were exposed to CL-20 for one or two weeks before dehydrogenase activity (DHA) or potential nitrification activity (PNA) were assayed. Results indicate that up to 10,000 mg kg(-1) soil of CL-20 had no statistically significant effects on microbial communities measured as DHA or on the ammonium oxidizing bacteria determined as PNA in both soils. Data indicates that CL-20 was not acutely toxic to the species or microbial communities tested and that further studies are required to address the potential long-term environmental impact of CL-20 and its possible degradation products.     

Sorption and oxic degradation of the explosive CL-20 during transport in subsurface sediments

The abiotic sorption and oxic degradation processes that control the fate of the explosive CL-20, Hexanitrohexaazaisowurtzitane, in the subsurface environment were investigated to determine the potential for vadose and groundwater contamination. Sorption of aqueous CL-20 is relatively small (K(d) = 0.02-3.83 cm3 g(-1) for 7 sediments and 12 minerals), which results in only slight retardation relative to water movement. Thus, CL-20 could move quickly through unsaturated and saturated sediments of comparable composition to groundwater, similar to the subsurface behavior of RDX. CL-20 sorption was mainly to mineral surfaces of the sediments, and the resulting isotherm was nonlinear. CL-20 abiotically degrades in oxic environments at slow rates (i.e., 10s to 100s of hours) with a wide variety of minerals, but at fast rates (i.e., minutes) in the presence of 2:1 phyllosilicate clays (hectorite, montmorillonite, nontronite), micas (biotite, illite), and specific oxides (MnO2 and the ferrous-ferric iron oxide magnetite). High concentrations of surface ferrous iron in a dithionite reduced sediment degraded CL-20 the fastest (half-life < 0.05 h), but 2:1 clays containing no structural or adsorbed ferrous iron (hectorite) could also quickly degrade CL-20 (half-life < 0.2 h). CL-20 degradation rates were slower in natural sediments (half-life 3-800 h) compared to minerals. Sediments with slow degradation rates and small sorption would exhibit the highest potential for deep subsurface migration. Products of CL-20 oxic degradation included three high molecular weight compounds and anions (nitrite and formate). The 2-3.5 moles of nitrite produced suggest CL-20 nitro-groups are degraded, and the amount of formate produced (0.2-1.2 moles) suggests the CL-20 cage structure is broken in some sediments. Identification of further degradation products and CL-20 mineralization rates is needed to fully assess the impact of these CL-20 transformation rates on the risk of CL-20 (and degradation product) subsurface movement.     

Monitoring of toxicity during degradation of selected pesticides using ionizing radiation

The optimization of experimental conditions for radiolytic removal of organic pollutants from water and waste with the use of ionizing radiation via controlling the concentration of target compound(s) requires also monitoring the toxicity changes during the process. Commonly used herbicides 2,4-D and dicamba were shown to increase toxicity measured with the Microtox test at low irradiation doses resulting from formation of more toxic transient products, which can be decomposed at larger doses. The changes of toxicity were examined with respect to dose magnitude and the presence of commonly occurring scavengers of radiation.     

Occurrence and abatement of volatile sulfur compounds during biogas production

Volatile sulfur compounds (VSCs) in biogas originating from a biogas production plant and from a municipal sewage water treatment plant were identified. Samples were taken at various stages of the biogas-producing process, including upgrading the gas to vehicle-fuel quality. Solid-phase microextraction was used for preconcentration of the VSCs, which were subsequently analyzed using gas chromatography in combination with mass spectrometry. Other volatile organic compounds present also were identified. The most commonly occurring VSCs in the biogas were hydrogen sulfide, carbonyl sulfide, methanethiol, dimethyl sulfide, and dimethyl disulfide, and hydrogen sulfide was not always the most abundant sulfur (S) compound. Besides VSCs, oxygenated organic compounds were commonly present (e.g., ketones, alcohols, and esters). The effect of adding iron chloride to the biogas reactor on the occurrence of VSCs also was investigated. It was found that additions of 500-g/m3 substrate gave an optimal removal of VSCs. Also, the use of a prefermentation step could reduce the amount of VSCs formed in the biogas process. Moreover, in the carbon dioxide scrubber used for upgrading the gas, VSCs were removed efficiently, leaving traces (ppbv levels). The scrubber also removed other organic compounds.     

Growth response to ozone of annual species from Mediterranean pastures

Ozone (O3) phytotoxicity has been reported on a wide range of plant species. However, scarce information has been provided regarding the sensitivity of semi-natural grassland species, especially those from dehesa Mediterranean grasslands, in spite of their great biological diversity and the high O3 levels recorded in the region. A screening study was carried out in open-top chambers (OTCs) to assess the O3-sensitivity of representative therophytes of these ecosystems based on the response of selected growth-related parameters. Three O3 treatments and 3 OTCs per treatment were used. Legume species were very sensitive to O3, because 78% of the tested species showed detrimental effects on their total biomass relative growth rate (RGR) following their exposure to O3. The Trifolium genus was particularly sensitive showing O3-induced adverse effects on most of the assessed parameters. Gramineae plants were less sensitive than Leguminosae species because detrimental effects on total biomass RGR were only observed in 14% of the assessed species. No relationship was found between relative growth rates when growing in clean air and O3 susceptibility. The implications of these effects on the performance of dehesa acidic grasslands and on the definition of ozone critical levels for the protection of semi-natural vegetation are discussed.     

Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis

A new analytical method has been developed for the quantification of 59 different persistent organohalogen compounds, such as polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), PCB metabolites, organochlorine pesticides (OCPs) in biological organ tissues. The optimum extraction and cleanup procedures were examined using accelerated solvent extraction (ASE), automated gel permeation chromatography (GPC) on Biobeads S-X3 and automated solid phase extraction (SPE) on silica-gel. The target compounds were divided into two fractions, non-polar compounds and more polar compounds, which in the latter fraction was subsequently methylated using diazomethane. Detection can be achieved by GC/MS in negative chemical ionization (NCI) mode. The average recoveries of the compounds spiked in swine liver, heart, kidney, and cattle adipose tissues were considered satisfactory, and it was confirmed that the method could be used in routine analysis.     

Source apportionment of indoor, outdoor, and personal PM2.5 in Seattle, Washington, using positive matrix factorization

As part of a large exposure assessment and health-effects panel study, 33 trace elements and light-absorbing carbon were measured on 24-hr fixed-site filter samples for particulate matter with an aerodynamic diameter <2.5 microm (PM2.5) collected between September 26, 2000, and May 25, 2001, at a central outdoor site, immediately outside each subject's residence, inside each residence, and on each subject (personal sample). Both two-way (PMF2) and three-way (PMF3) positive matrix factorization were used to deduce the sources contributing to PM2.5. Five sources contributing to the indoor and outdoor samples were identified: vegetative burning, mobile emissions, secondary sulfate, a source rich in chlorine, and a source of crustal-derived material. Vegetative burning contributed more PM2.5 mass on average than any other source in all microenvironments, with average values estimated by PMF2 and PMF3, respectively, of 7.6 and 8.7 microg/m3 for the outdoor samples, 4 and 5.3 microg/m3 for the indoor samples, and 3.8 and 3.4 microg/m3 for the personal samples. Personal exposure to the combustion-related particles was correlated with outdoor sources, whereas exposure to the crustal and chlorine-rich particles was not. Personal exposures to crustal sources were strongly associated with personal activities, especially time spent at school among the child subjects.