Variability in background levels of surface soil radionuclides in the vicinity of the US DOE waste isolation pilot plant

Concentrations of radionuclides were measured in soils from a grid of locations surrounding the US Department of Energy Waste Isolation Pilot Plant (WIPP) in southeastern New Mexico and from a grid on a reference site approximately 20 km southeast of the WIPP site. Each of the two grids has 16 sampling locations (grid nodes) systematically distributed within an area of 16.580 ha. Sampling was conducted prior to the arrival of the first waste shipment at WIPP. Thus, the 137Cs and 23,240Pu in the soil are expected to have been deposited as global fallout, although the Gnome Site, 8.8 km southwest of the WIPP, is also a potential source of 239,240Pu and fission products. The reference grid has significantly higher concentrations of fallout and natural radionuclides than the WIPP grid. Up to 80% of the total variability in radionuclide concentrations across the two grids is attributable to differences between grid nodes. Differences between replicates within a location account for 44-50% of the variability in concentrations of the uranium isotopes, but only 11-17% of the variability in the concentrations of the other radionuclides. Samples having similar abundance of radionuclides were spatially aggregated across the terrain. The activity concentrations of the radionuclides were strongly correlated with the concentrations of Al and Pb, and with the percentages of sand, silt and clay in the soil. Normalizing radionuclide concentrations to the concentration of Al or percent fine particles can help adjust for differences in soil textures among samples and facilitate the detection of gradients or temporal changes in soil concentrations.     

Improvement of thermal hydrolysis rate of dichloroacetic acid using alcohol

Dichloroacetic acid (DCAA) is produced during the oxidation of trichloroethylene. It is also produced in drinking water treatment as a disinfection by-product. DCAA is a problem material, because of its toxicity. The objective of this research is to find the final products and the reaction pathway of the DCAA decomposition by hydrolysis, and to increase the hydrolysis rate. The removal of both chlorine atoms in DCAA structure was achieved with hydrolysis at around 75 degrees C, and the final products were oxalic acid and glycolic acid. The reaction pathway was the production of oxalic acid and glycolic acid from two glyoxylic acid molecules by Cannizzaro reaction after the glyoxylic acid production from dechlorination of DCAA with hydrolysis. The hydrolysis rate of DCAA was increased with the use of 90% ethanol solution as solvent. The activation energy of DCAA was about 80 kJ/mol in it, while it was around 105 kJ/mol in water.     

Availability of 99Tc in undisturbed soil cores

Models for safety assessment of radioactive waste repositories need accurate values of the soil-to-plant transfer of radionuclides. In oxidizing environments, (99)Tc is expected to occur as pertechnetate ((99)TcO(4)(-)). Due to its high mobility, leaching of this element in the field might be important, potentially affecting the reliability of estimated transfer parameters of (99)Tc as measured in closed experimental systems such as hydroponics or pot experiments. The aim of this experiment was to measure the leaching of (99)Tc in undisturbed irrigated soil cores under cultivation as well as plant uptake and to study the possible competition between the two transfer pathways. Undisturbed soil cores (50 x 50 cm) were sampled from a Rendzic Leptosol (R), a colluvial Fluvic Cambisol (F) and a Dystric Cambisol (D) using PVC tubes (three cores sampled per soil type). Each core was equipped with a leachate collector at the bottom, allowing the monitoring of (99)Tc leaching through the cores. Cores were placed in a greenhouse and maize (Zea mays L., cv. DEA, Pioneer) was sown. After 135 d, maize was harvested and radioactivity determined in both plant and water samples. Results showed that during the growing period, leaching of (99)Tc was limited, due to the high evapotranspiration rate of maize. After harvest, leaching of (99)Tc went on because of the absence of evapotranspiration. Effective uptake (EU) of (99)Tc in leaves and grains was calculated. EU reached 70% of the input in the leaves and was not significantly different among soils. These results confirmed those obtained from pot experiments, even though leaching was allowed to occur in close-to-reality hydraulical conditions. As a consequence, it was concluded that pot experiments are an adequate surrogate for more complex "close-to-reality" experimental systems for measuring transfer factors.     

Chloroplastic responses of ponderosa pine (Pinus ponderosa) seedlings to ozone exposure

Integrity of chloroplast membranes is essential to photosynthesis. Loss of thylakoid membrane integrity has been proposed as a consequence of ozone (O(3)) exposure and therefore may be a mechanistic basis for decreased photosynthetic rates commonly associated with ozone exposure. To investigate this hypothesis, Pinus ponderosa seedlings were exposed to ambient air or ozone concentrations maintained at 0.15 or 0.30 microliter l(-1) for 10 h day(-1) for 51 days during their second growing season. Over the course of the study, foliage samples were periodically collected for thylakoid membrane, chlorophyll and protein analyses. Additionally, gas-exchange measurements were made in conjunction with foliage sampling to verify that observed chloroplastic responses were associated with ozone-induced changes in photosynthesis.Needles exposed to elevated ozone exhibited decreases in chlorophyll a and b content. The decreases were dependent on the duration and intensity of ozone exposure. When based on equal amounts of chlorophyll, ozone-exposed sample tissue exhibited an increase in total protein. When based on equal amounts of protein, ozone-exposed samples exhibited an increase in 37 kDa proteins, possibly consisting of breakdown products, and a possible decrease in 68 kDa proteins, Rubisco small subunit. There was also a change in the ratio of Photosystem I protein complexes CPI and CPII that may have contributed to decreased photosynthesis. Net photosynthetic rates were decreased in the high ozone treatment suggesting that observed structural and biochemical changes in the chloroplast were associated with alterations of the photosynthetic process.     

Human exposure to dioxins through the diet in Catalonia,Spain: carcinogenic and non-carcinogenic risk

The main objectives of this study were to estimate the dietary intake of dioxins by the population of Catalonia, Spain, to determine which food groups showed the greatest contribution to this intake, and to assess the health risks potentially associated with the dietary dioxin intake. From June to August 2000, food samples were randomly acquired in seven cities of Catalonia. Dioxin concentrations were determined in 108 samples belonging to the following groups: vegetables, fruits, pulses, cereals, fish and shellfish, meats and meat products, eggs, milk and dairy products, and oils and fats. Estimates of average daily food consumption were obtained from recent studies. Total dietary intake of dioxins for the general population of Catalonia was estimated to be 95.4 pg WHO-TEQ/day (78.4 pg I-TEQ/day), with fish and shellfish (31%), diary products (25%), cereals (14%) and meat (13%) showing the greatest percentages of contribution to dioxin intake. The contribution of all the rest of food groups to the total dietary intake was under 20%. The non-carcinogenic risk index of dioxin intake through the diet was in the range 0.34-1.36, while the carcinogenic risk level was 1,360 excess cancer over a lifetime of 70 years. Our results corroborate the decreasing tendency in dietary intake of dioxins found in recent studies (2000-2001) from various countries.     

Correlation of human olfactory responses to airborne concentrations of malodorous volatile organic compounds emitted from swine effluent

Direct multicomponent analysis of malodorous volatile organic compounds (VOCs) present in ambient air samples from 29 swine (Sus scrofa) production facilities was used to develop a 19-component artificial swine odor solution that simulated olfactory properties of swine effluent. Analyses employing either a human panel consisting of 14 subjects or gas chromatography were performed on the air stream from an emission chamber to assess human olfactory responses or odorant concentration, respectively. Analysis of the olfactory responses using Fisher's LSD statistics showed that the subjects were sensitive to changes in air concentration of the VOC standard across dilutions differing by approximately 16%. The effect of chemical synergisms and antagonisms on human olfactory response magnitudes was assessed by altering the individual concentration of nine compounds in artificial swine odor over a twofold concentration range while maintaining the other 18 components at a constant concentration. A synergistic olfactory response was observed when the air concentration of acetic acid was increased relative to the concentration of other VOC odorants in the standard. An antagonistic olfactory response was observed when the air concentration of 4-ethyl phenol was increased relative to the other VOC odorants in the standard. The collective odorant responses for nine major VOCs associated with swine odor were used to develop an olfactory prediction model to estimate human odor response magnitudes to swine manure odorants through measured air concentrations of indicator VOCs. The results of this study show that direct multicomponent analysis of VOCs emitted from swine effluent can be applied toward estimating perceived odor intensity.     

Exposure of workers in mineral processing industries in Brazil

The mining, milling and processing of uranium and thorium bearing minerals may result in radiation doses to workers. A preliminary survey pilot program, that included six mines in Brazil (two coal mines, one niobium mine, one nickel mine, one gold mine and one phosphate mine), was launched in order to determine the need to control the radioactive exposure of the mine-workers. Our survey consisted of the collection and analysis of urine samples, complemented by feces and air samples. The concentrations of uranium, thorium and polonium were measured in these samples and compared to background data from family members of the workers living in the same dwelling and from residents from the general population of Rio de Janeiro. The results from the coal mines indicated that the inhalation of radon progeny may be a source of occupational exposure. The workers from the nickel, gold and phosphate mines that were visited do not require a program to control internal radiological doses. The niobium mine results showed that in some areas of the industry exposure to thorium and uranium might occur.     

Review of ozone and temperature lidar validations performed within the framework of the Network for the Detection of Stratospheric Change

The use of assimilation tools for satellite validation requires true estimates of the accuracy of the reference data. Since its inception, the Network for Detection of Stratospheric Change (NDSC) has provided systematic lidar measurements of ozone and temperature at several places around the world that are well adapted for satellite validations. Regular exercises have been organised to ensure the data quality at each individual site. These exercises can be separated into three categories: large scale intercomparisons using multiple instruments, including a mobile lidar; using satellite observations as a geographic transfer standards to compare measurements at different sites; and comparative investigations of the analysis software. NDSC is a research network, so each system has its own history, design, and analysis, and has participated differently in validation campaigns. There are still some technological differences that may explain different accuracies. However, the comparison campaigns performed over the last decade have always proved to be very helpful in improving the measurements. To date, more efforts have been devoted to characterising ozone measurements than to temperature observations. The synthesis of the published works shows that the network can potentially be considered as homogeneous within +/-2% between 20-35 km for ozone and +/-1 K between 35-60 km for temperature. Outside this altitude range, larger biases are reported and more efforts are required. In the lower stratosphere, Raman channels seem to improve comparisons but such capabilities were not systematically compared. At the top of the profiles, more investigations on analysis methodologies are still probably needed. SAGE II and GOMOS appear to be excellent tools for future ozone lidar validations but need to be better coordinated and take more advantage of assimilation tools. Also, temperature validations face major difficulties caused by atmospheric tides and therefore require intercomparisons with the mobile systems, at all sites.     

Using surfactant-modified clays to determine sorption mechanisms for a representative organic base, quinoline

Sorption of a representative ionizable nitrogen heterocycle, quinoline (pKa = 4.92), was investigated to determine the relative contributions of the neutral and protonated species to the overall process. Batch sorption experiments were conducted on surfactant-modified clays that were synthesized from the exchange of hexadecyltrimethylammonium cations for resident sodium cations on a specimen smectite (Swy-2) at 0, 60, 80, and 100% of the clay's cation exchange capacity (CEC). Hexadecyltrimethylammonium exchange creates highly effective organic partitioning domains within the clay interlayers in proportion to their coverage on the exchange complex. The fractionally exchanged clays, therefore, provided discrete exchange and organic partitioning domains for the protonated and neutral species of quinoline. Data were described by a combined Langmuir-linear isotherm that permitted independent characterization of both sorption components. Results indicated that cationic sorption dominated but that the neutral species can contribute substantially given sufficient organic carbon content relative to the CEC and at pH above the pKa of quinoline. The data obtained in this study for quinoline demonstrated that the combined isotherm (including cation exchange and hydrophobic partitioning terms) describes sorption data and compares favorably with the purely empirical Freundlish isotherm.     

Relationships between soil and runoff phosphorus in small Alberta watersheds

Field-scale relationships between soil test phosphorus (STP) and flow-weighted mean concentrations (FWMCs) of dissolved reactive phosphorus (DRP) and total phosphorus (TP) in runoff are essential for modeling phosphorus losses, but are lacking. The objectives of this study were (i) to determine the relationships between soil phosphorus (STP and degree of phosphorus saturation (DPS)) and runoff phosphorus (TP and DRP) from field-sized catchments under spring snowmelt and summer rainfall conditions, and (ii) to determine whether a variety of depths and spatial representations of STP improved the prediction of phosphorus losses. Runoff was monitored from eight field-scale microwatersheds (2 to 248 ha) for 3 yr. Soil test phosphorus was determined for three layers (0 to 2.5 cm, 0 to 5 cm, and 0 to 15 cm) in spring and fall and the DPS was determined for the surface layer. Average STP (0 to 15 cm) ranged from 3 to 512 mg kg(-1), and DPS (0 to 2.5 cm) ranged from 5 to 91%. Seasonal FWMCs ranged from 0.01 to 7.4 mg L(-1) DRP and from 0.1 to 8.0 mg L(-1) TP. Strong linear relationships (r2=0.87 to 0.89) were found between the site mean STP and the FWMCs of DRP and TP. The relationships had similar extraction coefficients, intercepts, and predictive power among all three soil layers. Extraction coefficients (0.013 to 0.014) were similar to those reported for other Alberta studies, but were greater than those reported for rainfall simulation studies. The curvilinear DPS relationship showed similar predictive ability to STP. The field-scale STP relationships derived from natural conditions in this study should provide the basis for modeling phosphorus in Alberta.