Influence of quaternary ammonium on sorption of selected metal cations onto clinoptilolite zeolite

Clay minerals and zeolites have large cation exchange capacities, which enable them to be modified by cationic surfactant to enhance their sorption of organic and anionic contaminants. In this study, the influence of quaternary ammonium surfactants on sorption of five metal cations (Cs+, Sr+, La3+, Pb2+, and Zn2+) onto a clinoptilolite zeolite was investigated. Generally, the metal cation sorption capacity and affinity for the zeolite decreased, indicating that presorbed cationic surfactants blocked sorption sites for metal cations, as the surfactant loading on the zeolite increased. Cesium and Pb2+ sorption was affected to a small extent, indicating that selective sorption for Cs+ and specific sorption for Pb2+ play an important role in addition to cation exchange. Sorption of cationic surfactants on zeolite preloaded with different metal cations showed a strong correlation with the chain length of the surfactant tail group, while the roles of the charges and types of the metal cations were minimal. As the chain length increases, the critical micelle concentration decreases and the surfactant molecules become more hydrophobic, resulting in progressive bilayer coverage. Desorption of presorbed metal cations by cationic surfactants was strongly affected by the surfactant chain length and metal type. More metal cations, particularly Sr2+ and Zn2+, desorbed with an increase in surfactant chain length. The results, in combination with those from organic and oxyanion sorption on surfactant-modified zeolite, may be used for future surfactant modification to target sorption and desorption of a specific type of contaminant or a mixture of different types of contaminants.     

An analysis of the environmental mobility of radiostrontium from weapons testing and Chernobyl in Finnish river catchments

The mobility of radiostrontium within the Arctic environment and surrounding area has been studied by analysing the mobility of 90Sr in river catchments that are within Finland. The environmental mobility of 90Sr deposited by both nuclear weapons testing and the Chernobyl accident has been investigated in five Finnish river catchments. Different models assessing the time-dependent mobility of 90Sr have been evaluated. No significant differences were found between the mobility of 90Sr from nuclear weapons tests and from the Chernobyl accident. Model parameters obtained by fitting to the measurements of the deposition and runoff rates of the nuclear weapons test fallout gave predictions which were consistent with the mid- and long-term contamination by the Chernobyl fallout. A comparison of 90Sr with 137Cs showed that they had similar mobility on deposition but, as time passed, the relative mobility of 90Sr increased with respect to 137Cs over a period of 5-8 years. Once the relative migration of 90Sr with respect to 137Cs reached equilibrium, its runoff rate was, on average, approximately an order of magnitude greater than 137Cs.     

Assessing chronic toxicity of bisphenol A to larvae of the African clawed frog (Xenopus laevis) in a flow-through exposure system

A number of currently used industrial chemicals are estrogenic, and therefore have potential to disrupt sexual differentiation in vertebrate wildlife during critical developmental windows. We assessed the effect of larval exposure to bisphenol A (BPA) on growth, development and sexual differentiation of the gonad in the African Clawed frog, Xenopus laevis. Larvae were maintained in flow-through conditions at 22 +/- 1 degrees C and exposed to BPA at mean measured concentrations of 0.83, 2.1, 9.5, 23.8, 100, and 497 microg/l, from developmental stages 43/45-66 (completion of metamorphosis). Each test concentration, plus dilution water control (DWC) and positive control (17beta-estradiol (E2), 2.7 microg/l) employed four replicate test vessels with 40 larvae per tank. Individual froglets were removed from test vessels upon reaching stage 66, and the study was terminated at 90 days. Froglets were dissected and sex was determined by inspection of gross gonadal morphology. Test concentrations of BPA had no effect on survival, growth, developmental stage distributions at exposure days 32 and 62, or mean time to completion of metamorphosis, compared to DWC. Analysis of post-metamorphic sex ratio, determined by gross gonadal morphology, indicated no significant deviations from expected (50:50) sex ratio, in DWC or any BPA test concentration. In contrast, exposure of larvae to (E2) resulted in feminisation, with sex ratio deviating significantly (31% male, replicates pooled). Exposure to BPA in the concentration range 0.83-497 microg/l in flow-through conditions had no observable effect on larval growth, development or sexual differentiation (as determined by gross gonadal morphology) in this study.     

In vitro and in vivo studies of lead immobilization by synthetic hydroxyapatite

Apatite appears a useful compound for removing lead from water, due to its ability to immobilize the metal by precipitation. In dilute solution, dissolved hydroxyapatite [HA, Ca1O(P04)6(OH)2] provided phosphates that were reactive with aqueous lead (molar ratio HA/Pb= 1/10) forming precipitates at around pH 6. These dissolved at a more acidic pH (3). Solid HA in contact with Pb2+ions, led to the formation of pyromorphite [Pblo(P04)6(OH)2], identified by X-ray diffraction and insoluble at pH tested (3-8). The amount of pyromorphite increased with the weight ratio of HA/Pb. When this one increased from 1 to 1000, lead precipitated as pyromorphite rose from 19 to 99%. In vivo experiments on rats confirmed the in vitro results. In fact, lead bioavailability assessed by intestinal perfusion was unchanged in the presence of dissolved HA, whereas it was significantly lower in the presence of solid HA, evaluated by gastric intubation, at a weight ratio equal to 10 (amount of lead absorbed decreased by 60%). Apatite could bean effective means of immobilizing lead in drinking or sewage, since accidental pyromorphite ingestion does not yield bioavailable lead.     

Immobilization of iodide on copper(I) sulfide minerals

In the goal of finding efficient scavengers for radioiodide in conditions (pH, pE) close to those encountered in deep geological sites, sorption of iodide ions on cuprous sulfide minerals (especially roxbyite, Cu(1.75)S) has been studied. Surface analysis by X-ray photoelectron spectroscopy has shown that commercial cuprous sulfides are covered by an oxidized overlayer (mainly in the form of CuSO(4)). Therefore, a synthetic procedure to get roxbyite (typically by mixing Na(2)S with an aqueous suspension of commercial Cu(2)O) was applied to produce pure samples with clean surfaces. Batch equilibration of cuprous sulfide particles suspended in aqueous solutions containing iodide species has revealed significant consumption of iodide. The sorption mechanism involves the formation of a surface complex via the exchange of surface hydroxyl groups by iodide anions, as highlighted by a transient pH increase during the immobilization process. Other copper and mixed copper-iron sulfides (e.g. CuS, CuFeS(2)), which are stable over wide pH and potential ranges are also likely to accumulate iodide species. Because of the specific interaction between iodide and copper(I) centers on the minerals, high distribution coefficients (>1000 ml/g) were observed.     

Principles and issues in radiological ecological risk assessment

This paper provides a bridge between the fields of ecological risk assessment (ERA) and radioecology by presenting key biota dose assessment issues identified in the US Department of Energy's Graded Approach for Evaluating Radiation Doses to Aquatic and Terrestrial Biota in a manner consistent with the US Environmental Protection Agency's framework for ERA. Current radiological ERA methods and data are intended for use in protecting natural populations of biota, rather than individual members of a population. Potentially susceptible receptors include vertebrates and terrestrial plants. One must ensure that all media, radionuclides (including short-lived radioactive decay products), types of radiations (i.e., alpha particles, electrons, and photons), and pathways (i.e., internal and external contamination) are combined in each exposure scenario. The relative biological effectiveness of alpha particles with respect to deterministic effects must also be considered. Expected safe levels of exposure are available for the protection of natural populations of aquatic biota (10 mGy d(-1)) and terrestrial plants (10 mGy d(-1)) and animals (1 mGy d(-1)) and are appropriate for use in all radiological ERA tiers, provided that appropriate exposure assumptions are used. Caution must be exercised (and a thorough justification provided) if more restrictive limits are selected, to ensure that the supporting data are of high quality, reproducible, and clearly relevant to the protection of natural populations.     

Effects of alum and aluminum chloride on phosphorus runoff from swine manure

Phosphorus (P) runoff from fields fertilized with swine (Sus scrofa domesticus) manure may contribute to eutrophication. The objective of this study was to evaluate the effect of aluminum sulfate (alum) and aluminum chloride applications to swine manure on P runoff from small plots cropped to tall fescue (Festuca arundinacea Shreb.). There were six treatments in this study: (i) unfertilized control plots, (ii) untreated manure, (iii) manure with alum at 215 mg Al L(-1), (iv) manure with aluminum chloride at 215 mg Al L(-1), (v) manure with alum at 430 mg Al L(-1), and (vi) manure with aluminum chloride at 430 mg Al L(-1). Manure application rates were equivalent to approximately 125 kg N ha(-1). Alum and aluminum chloride additions lowered soluble reactive phosphorus (SRP) levels from about 130 mg P L(-1) to approximately 30 mg P L(-1) at low rates. At high rates, SRP levels in swine manure were around 1 mg P L(-1). Soluble reactive P concentrations in runoff were 5.50, 3.66, 3.00, 0.87, 0.87, and 0.55 mg P L(-1), for normal manure, low alum, low aluminum chloride, high alum, high aluminum chloride, and unfertilized control plots, respectively. Hence, high alum and aluminum chloride reduced SRP concentrations in runoff by 84% and were not statistically different from SRP concentrations in runoff from unfertilized control plots. These data indicate that treating swine manure with alum or aluminum chloride could result in significant reductions in nonpoint-source P runoff.     

Effect of culture conditions on the formation of struvite by Myxococcus xanthus

The amount of struvite (MgNH₄PO₄·6H₂O) produced by Myxococcus xanthus as well as the culture parameter values (pH, total phosphorus, total Kjeldahl nitrogen) were dependent on the culture medium used. Struvite formation started during the exponential phase and the maximum concentration was observed at the beginning of stationary growth phase. The addition of each medium component to the liquid culture influenced the amount of crystal produced. This amount did not depend on the pH increase during the culture period. The moment of the bacterial growth phase, at which each medium component was added, influenced the struvite formation.     

Global factors shaping the future of food aid: the implications for WFP

Food aid is a key component of a humanitarian response but its use in other programming contexts is subject to numerous criticisms. Even in humanitarian emergencies food aid is often late, unreliable and out of proportion to other elements of the response. Three major factors will shape the future of food aid. First, mechanisms of food aid governance are being reviewed and may undergo major changes—particularly the Food Aid Convention now that hopes have diminished for an Agreement on Agriculture at the World Trade Organisation. The second significant factor is donor agency trends. Overall levels of food aid have dropped fairly steadily in recent decades and there are several discernible trends in resource allocation, procurement and the use of food aid. The third factor is an emerging body of best practice that will define acceptable standards of food aid programming in the future.     

Vapor flammability above aqueous solutions of flammable liquids

The flammability of vapors above aqueous solutions of ethanol and acetonitrile was studied experimentally in a 20-L combustion apparatus. No liquid was present in the apparatus, but the vapor concentrations were adjusted to correspond to the vapor in equilibrium with a specified aqueous solution. The experimental results for these two systems show that

• As water is added to the vapor, the lower boundary of the flammability zone decreases. For ethanol, the lower flammability limits (LFL) decreases from 3.7% for pure vapor to 3.2% with saturated water vapor. For acetonitrile, the decrease is from 4.2% to 3.8%. Thus, to a good approximation, the water vapor can be treated as an inert, enabling the data to be displayed on a single flammability triangle diagram. This provides a very simplified method for estimating the flammable behavior for aqueous solutions.

• The upper boundary of the flammability zone is unchanged with the addition of water.

• The limiting oxygen concentration (LOC) is essentially constant for all concentrations of aqueous solutions. The LOC for the pure solvent may be used as a universal LOC for all solvent concentrations.

• The vapor mixture above the aqueous solution is not flammable below a certain liquid mol fraction of flammable. The flammable concentration at which this occurs can be called the maximum safe solvent concentration (MSSC). A method is presented to determine the MSSC from experimental flammability data.

• The oxygen concentration defining the flammable boundary for the vapor decreases rapidly from the MSSC and then increases as the liquid solvent concentration increases.

The calculated adiabatic flame temperature (CAFT) method qualitatively predicts the same behavior as the experimental data.