Particulate and dissolved elemental loads in the Kuji River related to discharge rate

In order to investigate influences of discharge rates on fluvial transport behavior of elements in the Kuji River, Japan, suspended and dissolved phase concentrations in the river water were measured together with the water flow rates. The concentrations of suspended particulate matter (SPM) increased by two or three orders of magnitude with the water discharge, and also had seasonal variations. Adsorptive elements or heavy metal elements, which tend to form insoluble compounds, were present generally as suspended forms in the river waters, and their dissolved form concentrations tended to increase with the water discharge. On the other hand, non-adsorptive elements such as alkali and alkaline-earth elements were present as dissolved forms under a normal flow rate condition, but equivalent quantity of suspended species also occurred under a high flow condition. In this case, the dissolved form concentrations decreased with the water discharge. Characterization of SPM with analyses of chemical compositions, scanning electron microscopy (SEM) and X-ray diffractometry (XRD) indicated that clay mineral such as montmorillonite would be the main carrier material of trace and major elements during the fluvial transport in the Kuji River. Variations of contents of selected elements in SPM with the water discharge indicated that river bottom sediments, which are probably potential sources of SPM added due to high water flow rates, would be different in chemical compositions from SPM floating under a normal flow condition. Variations of chemical compositions of SPM as well as of suspended or dissolved form concentrations of elements in the river waters were formulated as a function of the water discharge rates.     

Anthropogenic 236U at Rocky Flats,Ashtabula river harbor,and Mersey estuary: three case studies by sector inductively coupled plasma mass spectrometry

236U (t(1/2)=2.3 x 10(7) y) is formed as a result of thermal neutron capture by (235)U. In naturally occurring U ores, where a high neutron flux is present from spontaneous fission of (238)U, (236)U/(238)U atom ratios are approximately 10(-4) ppm. In the natural Earth's crust, unaffected by nuclear fallout, these ratios are expected to be on the order of 10(-8) ppm. Reactor-irradiated U, however, exhibits high (236)U/(238)U atom ratios approaching 10(4) ppm. As a result, the presence of very small quantities of reactor-irradiated U will significantly enhance the "background" (236)U/(238)U atom ratio. When sufficiently elevated (236)U/(238)U ratios are present, the determination of (236)U/(238)U by rapid inductively coupled plasma mass spectrometric (ICPMS) methods is attractive. We have used sector ICPMS at medium resolving power (R=3440) to measure (236)U/(238)U atom ratios with a determination limit of 0.2 ppm. The limiting factors in the measurement are the (235)U(1)H(+) isobar and background signal at m/z 236 arising from the (238)U(+) peak tail. Based upon the analysis of replicates and considerations of possible systematic errors, uncertainties of +/-5% are found for (236)U/(238)U atom ratios of 1-100 ppm. This procedure has been demonstrated in studies of anthropogenic (236)U in the environment at three locations: (a) offsite soils from the vicinity of the Rocky Flats Environmental Technology site (Golden, Colorado, USA); (b) sediments from the Ashtabula River (Ohio, USA); and (c) sediments from the Mersey estuary (Liverpool, UK). In each of these three locations, definite plumes of elevated (236)U/(238)U are identified and characterized. Maximum (236)U/(238)U atom ratios observed in RFETS-vicinity soils, the Ashtabula River, and the Mersey Estuary are 2.8, 140, and 4.4 ppm, respectively.     

Temporal variation of 137Cs water column inventory in the North Pacific since the 1960s

The temporal variation of water column inventories of 137Cs in the North Pacific since the 1960s was examined based on the analysis of the 137Cs profiles in HAM database. 137Cs in seawater in the North Pacific have originated mainly from global fallout from atmospheric nuclear weapons tests, which occurred in the early 1960s. In the 1960s, both the meridional distribution of 137Cs inventory in the North Pacific and that of fallout on land stations showed mid-latitude maximum. The region with higher deposition at land stations, however, was more northern than the latitudes where the 137Cs inventory in the North Pacific showed a maximum. The difference of the latitude where maximum 137Cs deposition/inventory was observed reflects the difference of the geographical distribution of the precipitation amount in the Pacific and Atlantic Oceans followed by the different warm current systems in each ocean. A good positive relation between 137Cs inventory and annual precipitation amount was discovered in the ocean stations at the middle latitude in the North Pacific. The horizontal distribution of 137Cs inventories at the middle latitudes in the North Pacific is characterized as west-high and east-low in the early 1960s, which was basically controlled by the distribution of annual precipitation amount. Eastward advection, then, modified it to be less difference in 1966-1967 after the highest deposition periods in 1963-1965. In the 1970s and 1980s, increases of the 137Cs inventory at the lower latitude of 10-20 deg. N are found. Surface and subsurface southward transports are considered as the source of this increasing 137Cs inventory.     

A kinetic-allometric approach to predicting tissue radionuclide concentrations for biota

Allometry, or the biology of scaling, is the study of size and its consequences. It has become a useful tool for comparative physiology. There are several allometric equations that relate body size to many parameters, including ingestion rate, lifespan, inhalation rate, home range and more. While these equations were originally derived from empirical observations, there is a growing body of evidence that these relationships have their origins in the dynamics of energy transport mechanisms. As part of an ongoing effort by the Department of Energy in developing generic methods for evaluating radiation dose to biota, we have examined the utility of applying allometric techniques to predicting radionuclide tissue concentration across a large range of terrestrial and riparian species of animals. This particular study examined 23 radionuclides. Initial investigations suggest that the allometric approach can provide a useful tool to derive limiting values of uptake and elimination factors for animals.     

Use of HPGe gamma-ray spectrometry to assess the isotopic compositiion of uranium in soils

Gamma-ray spectrometry was used to determine uranium activity and investigate the presence of depleted uranium in soil samples collected from camping sites of the Greek expeditionary force in Kosovo. Assessment of 238U concentrations was based on measurements of the 63.3 keV and 92.38 keV emissions of its first daughter nuclide, 234Th. To determine the isotopic ratio of 238U/235U, secular equilibrium along the two radioactive series was first ensured and thereby the contribution of 235U under the 186 keV peak was deduced. The uranium activity in the samples varied from 48 to 112 Bq kg(-1), whereas the activity ratio of 238U/235U averaged 23.1+/-4.3.     

Removal of uranium(VI) from contaminated sediments by surfactants

Uranium(VI) sorption onto a soil collected at the Melton Branch Watershed (Oak Ridge National Laboratory, TN) is strongly influenced by the pH of the soil solution and, to a lesser extent, by the presence of calcium, suggesting specific chemical interactions between U(VI) and the soil matrix. Batch experiments designed to evaluate factors controlling desorption indicate that two anionic surfactants, AOK and T77, at concentrations ranging from 60 to 200 mM, are most suitable for U(VI) removal from acidic soils such as the Oak Ridge sediment. These surfactants are very efficient solubilizing agents at low uranium concentrations: ca. 100% U(VI) removal for [U(VI)]o,sorbed = 10(-6) mol kg-1. At greater uranium concentrations (e.g., [U(VI)]o,sorbed = ca. 10(-5) mol kg-1), the desorption efficiency of the surfactant solutions increases with an increase in surfactant concentration and reaches a plateau of 75 to 80% of the U(VI) initially sorbed. The most probable mechanisms responsible for U(VI) desorption include cation exchange in the electric double layer surrounding the micelles and, to a lesser extent, dissolution of the soil matrix. Limitations associated with the surfactant treatment include loss of surfactants onto the soil (sorption) and greater affinity between U(VI) and the soil matrix at large soil to liquid ratios. Parallel experiments with H2SO4 and carbonate-bicarbonate (CB) solutions indicate that these more conventional methods suffer from strong matrix dissolution with the acid and reduced desorption efficiency with CB due to the buffering capacity of the acidic soil.     

Sorption of polycyclic aromatic compounds to humic and fulvic acid HPLC column materials

Two different humic acids (HA) and a fulvic acid (FA) were chemically immobilized to a high performance liquid chromatography (HPLC) silica column material. The immobilization was performed by binding amino groups in HA/FA to the free aldehyde group in glutardialdehyde attached to the silica gel. The HPLC column materials were compared with a blank column material made by applying the same procedure but without immobilizing HA or FA. Also, a column was made by binding carbonyl groups in HA to amino groups attached to the silica gel. The humic substances were selected to secure appropriate variation of their structural features. The retention factors of 45 polycyclic aromatic compounds (PAC) to the four columns were determined by HPLC. The advantage of the technique is a large number of compounds can easily be studied. The binding procedure does not appear to cause a drastic selection between the HA molecules. The k' values obtained for the two Aldrich HA columns agree in general reasonably. The retention or sorption of the compounds increased with the size of the PAC and the number of lipophilic substituents, but decreased when polar substituents were present. The PAC retention was much stronger to the two HA columns than to the FA and blank column, both for hydrophobic polycyclic aromatic hydrocarbons (PAH) and the polar PAC. Other factors impacting the PAC binding may be specific interactions with HA and the ionic strength of the aqueous phase. The technique has been applied to do direct determinations of Koc.     

Phytoremediation of aged petroleum sludge: effect of irrigation techniques and scheduling

The use of higher plants to accelerate the remediation of petroleum contaminants in soil is limited by, among other factors, rooting depth and the delivery of nutrients to the microsites at which remediation occurs. The objective of this study was to test methods of enhancing root growth and remediation in the subsurface of a contaminated petroleum sludge. The phytoremediation of highly contaminated petroleum sludge (total petroleum hydrocarbons >35 g kg(-1) was tested in the greenhouse as a function of the frequency and the depth of irrigation and fertilization. Water and dissolved plant nutrients were added to the soil surface or at a depth of 30 cm, either daily or weekly. Equivalent quantities of water and nutrients were added in all cases. Daily irrigation at a depth of 30 cm invoked greater root growth and enhanced contaminant degradation relative to all other treatments. In the absence of plants, residual concentrations of petroleum hydrocarbons after 7 mo were higher than with plants. The presence of plant roots clearly improved the physical structure of the soil and increased microbial populations. Thus, the plant roots in conjunction with daily additions of soluble N and P appeared to enhance oxygen transport to greater depths in the soil, stimulate petroleum-degrading microorganisms, and provide microbial access to soil micropores. Subsurface irrigation with frequent, small amounts of water and nutrients could significantly accelerate phytoremediation of field soils contaminated with petroleum hydrocarbons.     

ESF Workshop

Dioxin and PCB monitoring programs for food and feeding stuff in most countries of the world, including many European Countries are currently inadequate. Better control of food production lines and food processing procedures is needed to minimize entry of dioxin to the food chain and will help to avoid dioxin contamination accidents. This would also improve the ability to trace back a possible contamination to its source. European guidelines for monitoring programs should be established to ensure comparable and meaningful results. These guidelines should define the minimum requirements for the design of monitoring programs, analytical methods, and quality assurance. Though data from Northern Europe shows that the general population exposure to dioxin and PCB has decreased during the last ten years these compounds continue to be a risk of accidental contamination of the food chain. The most prominent recent example is the Belgian dioxin contamination of feeding stuff in 1999. The Belgian dioxin contamination was not detected due to dioxin monitoring programs but by their direct biological effects seen in animals. Four other cases of dioxin contamination have been detected in Europe since 1997 due to local monitoring programs. One of them (citrus pulp pellets 1998) was in a much larger scale than the Belgian dioxin contamination. The general population's exposure to dioxins and PCBs is still in the same range (1-4 pg WHO-TEQ/kg body weight and day) as the recently revised WHO tolerable daily intake (TDI). There is concern that short-term high level exposure to dioxins, furans, and PCB may cause biological effects on the human fetal development and further research is required. Further actions to control sources building on considerable advances already made in many countries may need to be supplemented by measures to prevent direct contamination of feeding stuff or food to reduce general population exposure further.     

Relationships between ambient geochemistry, watershed land-use and trace metal concentrations in aquatic invertebrates living in stormwater treatment ponds

Stormwater treatment ponds receive elevated levels of metals from urban runoff, but the effects of these pollutants on organisms residing in the ponds are unknown. We investigated the accumulation of Cu, Zn, and Pb by macroinvertebrates collected from stormwater treatment ponds in Maryland serving commercial, highway, residential and open-space watersheds, and determined whether watershed land-use classification influences metal concentrations in macroinvertebrates, sediments, and water. Three types of invertebrate samples were analyzed--molluscs, odonates, and composite. Zn concentrations in odonates from ponds draining watersheds with commercial development (mean = 113.82 micrograms g-1) were significantly higher than concentrations in the other land-use categories. Similarly, Cu levels in odonates from commercial ponds (mean = 27.12 micrograms g-1) were significantly higher than from highway (mean = 20.23 micrograms g-1) and open space (mean = 17.79 micrograms g-1) ponds. However, metal concentrations in sediments and water did not differ significantly among land-uses. The results suggest that despite the high variation in ambient metal concentrations within each land-use category, macroinvertebrates in ponds serving commercial watersheds accumulate higher levels of Cu and Zn. The levels of Cu, Zn, and Pb in invertebrates from all ponds were less than dietary concentrations considered toxic to fish.