Cs, Pu concentrations and the Pu/Pu atom ratio in a sediment core from the sub-aqueous delta of Yangtze River estuary

A sediment core collected from the sub-aqueous delta of the Yangtze River estuary was subjected to analyses of ¹³⁷Cs and plutonium (Pu) isotopes. The ¹³⁷Cs was measured using γ-spectrometry at the laboratories at the Nanjing University and Pu isotopes were determined with Accelerator Mass Spectrometry (AMS), measurements made at the Australian National University. The results show considerable structure in the depth concentration profiles of the ¹³⁷Cs and ^239+240Pu. The shape of the vertical ¹³⁷Cs distribution in the sediment core was similar to that of the Pu. The maximum ¹³⁷Cs and ^239+240Pu concentrations were 16.21 ± 0.95 mBq/g and 0.716 ± 0.030 mBq/g, respectively, and appear at same depth. The average ²⁴⁰Pu/²³⁹Pu atom ratio was 0.238 ± 0.007 in the sediment core, slightly higher than the average global fallout value. The changes in the ²⁴⁰Pu/²³⁹Pu atom ratios in the sediment core indicate the presence of at least two different Pu sources, i.e., global fallout and another source, most likely close-in fallout from the Pacific Proving Grounds (PPG) in the Marshall Islands, and suggest the possibility that Pu isotopes are useful as a geochronological tool for coastal sediment studies. The ¹³⁷Cs and ^239+240Pu inventories were estimated to be 7100 ± 1200 Bq/m² and 407 ± 27 Bq/m², respectively. Approximately 40% of the ^239+240Pu inventory originated from the PPG close-in fallout and about 50% has derived from land-origin global fallout transported to the estuary by the river. This study confirms that AMS is a useful tool to measure ²⁴⁰Pu/²³⁹Pu atom ratio and can provide valuable information on sedimentary processes in the coastal environment.     

Detection of tritium sorption on four soil materials

In order to measure groundwater age and design nuclear waste disposal sites, it is important to understand the sorption behavior of tritium on soils. In this study, batch tests were carried out using four soils from China: silty clays from An County and Jiangyou County in Sichuan Province, both of which could be considered candidate sites for Very Low Level Waste disposal; silty sand from Beijing; and loess from Yuci County in Shanxi Province, a typical Chinese loess region. The experimental results indicated that in these soil media, the distribution coefficient of tritium is slightly influenced by adsorption time, water/solid ratio, initial tritium specific activity, pH, and the content of humic and fulvic acids. The average distribution coefficient from all of these influencing factors was about 0.1-0.2 mL/g for the four types of soil samples. This relatively modest sorption of tritium in soils needs to be considered in fate and transport studies of tritium in the environment.     

Depth profile of ²³⁶U/²³⁸U in soil samples in La Palma, Canary Islands

The vertical distribution of the ²³⁶U/²³⁸U isotopic ratio was investigated in soil samples from three different locations on La Palma (one of the seven Canary Islands, Spain). Additionally the ²⁴⁰Pu/²³⁹Pu atomic ratio, as it is a well establish tool for the source identification, was determined. The radiochemical procedure consisted of a U separation step by extraction chromatography using UTEVA^® Resin (Eichrom Technologies, Inc.). Afterwards Pu was separated from Th and Np by anion exchange using Dowex 1x2 (Dow Chemical Co.). Furthermore a new chemical procedure with tandem columns to separate Pu and U from the matrix was tested. For the determination of the uranium and plutonium isotopes by alpha spectrometry thin sources were prepared by microprecipitation techniques. Additionally these fractions separated from the soil samples were measured by Accelerator Mass Spectrometry (AMS) to get information on the isotopic ratios ²³⁶U/²³⁸U, ²⁴⁰Pu/²³⁹Pu and ²³⁶U/²³⁹Pu, respectively. The ²³⁶U concentrations [atoms/g] in each surface layer (∼2 cm) were surprisingly high compared to deeper layers where values around two orders of magnitude smaller were found. Since the isotopic ratio ²⁴⁰Pu/²³⁹Pu indicated a global fallout signature we assume the same origin as the probable source for ²³⁶U. Our measured ²³⁶U/²³⁹Pu value of around 0.2 is within the expected range for this contamination source.     

An occupational exposure assessment of polychlorinated dibenzo-p-dioxin and dibenzofurans in firefighters

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are unintentional byproducts of combustion and industrial processes. Firefighters face the risk of occupational exposure to PCDD/Fs. Congener-specific analyses of 17 PCDD/Fs were performed on 20 serum samples collected from firefighters and fire scene investigators, and four soot samples that had deposited on the surfaces of the fire helmets and were collected after the firefighters had fought fires. The PCDD/F concentrations on the helmets that were contaminated by being worn at the fire scenes were 63-285 times higher than those on a clean helmet. The median serum PCDD/F concentration of the 16 firefighters (12 pg WHO₂₀₀₅-TEQ g⁻¹ lipid) was not different from those of the males from the general Taiwanese population (9.4 pg WHO₂₀₀₅-TEQ g⁻¹ lipid). However, the median PCDD/F level in the four fire scene investigators (15 pg WHO₂₀₀₅-TEQ g⁻¹ lipid) was higher than those in the male from the general Taiwanese population (Mann-Whitney U test, p < 0.01). Furthermore, the serum samples from the firefighters and fire scene investigators, and the soot samples from the fire scenes presented similarly distinctive PCDD/F profiles that had elevated proportions for 10 PCDF congeners. Limited data indicated that the fire scene investigators were occupationally exposed to PCDD/Fs at the fire scenes. We suggested that the firefighters were not occupationally exposed to PCDD/Fs at the fire scenes due to appropriate protection. However, the fire scene investigators may have had more occupational exposure to PCDD/Fs due to poor protection, and further research must be performed to confirm this.     

Global Urban Growth and the Geography of Water Availability,Quality, and Delivery

Globally, urban growth will add 1.5 billion people to cities by 2030, making the difficult task of urban water provisions even more challenging. In this article, we develop a conceptual framework of urban water provision as composed of three axes: water availability, water quality, and water delivery. For each axis, we calculate quantitative proxy measures for all cities with more than 50,000 residents, and then briefly discuss the strategies cities are using in response if they are deficient on one of the axes. We show that 523 million people are in cities where water availability may be an issue, 890 million people are in cities where water quality may be an issue, and 1.3 billion people are in cities where water delivery may be an issue. Tapping into groundwater is a widespread response, regardless of the management challenge, with many cities unsustainably using this resource. The strategies used by cities deficient on the water delivery axis are different than for cities deficient on the water quantity or water quality axis, as lack of financial resources pushes cities toward a different and potentially less effective set of strategies.     

Salting-out phenomenon and 1-octanol/water partition coefficient of metalaxyl pesticide

In this paper, we present the effect of inorganic cations such as Na⁺, K⁺, Ca²⁺, Mg²⁺ on the salting-out phenomenon of metalaxyl from pure water to aqueous salt solutions. Moreover the 1-octanol/water partition coefficient in pure water is presented. To accomplish this, aqueous solubility of metalaxyl was determined in pure water, in different salt solution (NaCl, KCl, CaCl₂ and MgCl₂), and at different concentration level ranging from 0.01 to 1.5 M. The 1-octanol/water partition coefficient was determined using the static shake-flask method. Solubility was determined using dynamic saturation method for pure water in the range of 298.15-325.15 K and at 298.15 K for different salt solutions. The solubility value in pure water for studied interval was found constant (m = 3.118 × 10⁻² mol kg⁻¹).Solubility values were used to calculate the standard molar Gibbs free energy of dissolution (Δ_solG°) and transfer (Δ_trG°) at 298.15 K. The values of Δ_trG° from pure to all studied aqueous salt solutions did not exceed 2 kJ mol⁻¹, the value of Δ_solG° of dissolution is 18.5 ±0.72 kJ mol⁻¹. The 1-octanol/water partition coefficient in pure water log K_o/w is equal to 1.69. The obtained results confirm the classification of the neutral metalaxyl as a slightly hydrophobic molecule.     

Viable skin efficiently absorbs and metabolizes bisphenol A

Skin contact has been hypothesized to contribute to human exposure to bisphenol A (BPA). We examined the diffusion and metabolism of BPA using viable skin models: human skin explants and short-term cultures of pig ear skin, an alternative model for the study of the fate of xenobiotics following contact exposure. ¹⁴C-BPA [50-800 nmol] was applied on the surface of skin models. Radioactivity distribution was measured in all skin compartments and in the diffusion cells of static cells diffusion systems. BPA and metabolites were further quantified by radio-HPLC. BPA was efficiently absorbed in short-term cultures, with no major difference between the models used in the study [viable pig ear skin: 65%; viable human explants: 46%; non-viable (previously frozen) pig skin: 58%]. BPA was extensively metabolized in viable systems only. Major BPA metabolites produced by the skin were BPA mono-glucuronide and BPA mono-sulfate, accounting together for 73% and 27% of the dose, in pig and human, respectively. In conclusion, experiments with viable skin models unequivocally demonstrate that BPA is readily absorbed and metabolized by the skin. The trans-dermal route is expected to contribute substantially to BPA exposure in human, when direct contact with BPA (free monomer) occurs.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

Fate of bisphenol A during treatment with the litter-decomposing fungi Stropharia rugosoannulata and Stropharia coronilla

Bisphenol A is an endocrine disrupting compound, which is ubiquitous in the environment due to its wide use in plastic and resin production. Seven day old cultures of the litter-decomposing fungus Stropharia coronilla removed the estrogenic activity of bisphenol A (BPA) rapidly and enduringly. Treatment of BPA with purified neutral manganese peroxidase (MnP) from this fungus also resulted in 100% reduction of estrogenic activity, as analyzed using a bioluminescent yeast assay, and in the formation of polymeric compounds. In cultures of Stropharia rugosoannulata, estrogenic activity also quickly disappeared but temporarily re-emerged in the further course of cultivation. LC-MS analysis of the extracted estrogenic culture liquid revealed [M−H]⁻ ions with m/z values of 219 and 235. We hypothesize that these compounds are ring fission products of BPA, which still exhibit one intact hydroxyphenyl group to interact with estrogen receptors displayed by the yeast.