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.     

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.     

Risk assessment and pathway study of arsenic in industrially contaminated sites of Hyderabad: a case study

Different areas in the industrial region of Patancheru near Hyderabad, Andhra Pradesh (A.P), India are contaminated with high concentration of arsenic, which is attributed to industrial source like veterinary chemicals, pharmaceuticals, pesticide industries, etc. Fourteen villages of this area of Patancheru were assessed for arsenic contamination by collecting samples of water (surface and ground), soil, fodder, milk, and vegetables. The total arsenic content in the whole blood, urine, hair, and nails of the residents showing arsenical skin lesions and other clinical manifestations were also studied. To understand the bioavailability of arsenic in this environment and its possible entry into human food chain, speciation studies of arsenic was carried out and the results are presented in this paper.     

Dissipation and mobility of permethrin in the field with repeated applications under tropical conditions

Studies on persistence, mobility and the effect of repeated application of permethrin on its half-life were carried out under field conditions. The half-life of permethrin in the top 20 cm of the soil increased from 11.5 to 23.6 days as the application rates increased from 35 to 140 g ha(-1). Induced by heavier rainfall, more residues moved downward in trial 2 than in trial 1. Repeated applications enhanced degradation rates and mobility of permethrin in the soil. The residue level in the 0-5-cm layer was reduced at day 28 after 17 consecutive applications to a level lower than after 5 applications. The half-life of permethrin was reduced from 15.9 days to 11.2 days after 5 and 17 applications, respectively. The residue reached the 15-20 cm layer much earlier (approximately 3 days after treatment) in soil that received 17 applications as compared to those with two applications.     

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.     

Phosphorus sorption characteristics of estuarine sediments under different redox conditions

Phosphorus (P) plays a major role in eutrophication of aquatic systems. Estuarine sediments could function as sources or sinks for P to the overlying water column depending upon their physico-chemical characteristics. Understanding of P sorption phenomena in estuarine sediments is important in regulating the P availability in estuaries. Phosphorus sorption characteristics of sediments from the Indian River Lagoon, Florida, USA, were determined to examine the role of selected physico-chemical properties of the sediments on soluble reactive P status in estuary water. Mean equilibrium P concentrations (EPCo) of 0.75 mg L(-1) and mean P sorption maxima (Smax) of 32.2 mg kg(-1) were obtained under anaerobic conditions, compared with EPCo of 0.05 mg L(-1) and Smax of 132.7 mg kg(-1) under aerobic conditions. The higher EPCo values under anaerobic conditions and the greater Smax values under aerobic conditions were associated with amorphous and poorly crystalline iron. These results suggest that sediments enriched with amorphous and poorly crystalline forms of iron act as an excellent reservoir for P by adsorbing excessive P in aerobic sediment zones and releasing it upon burial under anaerobic conditions. This study also indicates that P compounds in sediments independently maintain equilibrium with P in solutions. Thus, heterogeneous systems like soil and sediment simply behave as a mixture of homogeneous surfaces as far as their P sorption characteristics are concerned, and hence can be successfully described by the Langmuir and Freundlich models.     

Residents' perceptions of water quality improvements following remediation work in the Pymme's Brook catchment, north London, UK

Residents' perceptions of water quality change following remediation work in the upper Pymme's Brook catchment (north London) were elicited by questionnaire and compared with monitored changes in Escherichia coli count and BMWP (The Biological Monitoring Working Party (BMWP)) score. The wider usefulness of consumer perception surveys was then discussed. Monthly data collected between 1990 and 1996 shows that both E. coli count and BMWP score improved following flushing of the foul sewerage system in 1992, but that only E. coli count improved following the subsequent completion of large-scale remedial engineering works. Local residents were surveyed regarding their awareness of the scheme, and the causes of pollution, together with their perceptions as to the effects of the engineering works and of the resulting water quality improvements. Most respondents selected and ranked indicators in a way that suggested they had an awareness of the significance of various indicators of pollution severity. Following completion of the remediation scheme, residents perceived the watercourse to contain less rubbish and sewage fungus, and to have an improved colour and smell, which corresponds favourably to the monitored improvements. However, respondents' perceptions were found to vary when the study population was sub-divided using a range of parameters. For instance, frequent observers of the brook were most likely to correctly identify sewage as the main form of pollution. These divergent perceptions suggest that there may be considerable difficulties when perception surveys are used to quantify 'benefits' following environmental improvement programmes. Nevertheless, the survey was clearly beneficial in enhancing residents' awareness of their environment and the role of their voice in its management.     

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.