Selective uptake of thorium(IV) from nitric acid medium using two extraction chromatographic resins based on diglycolamide-calix[4]arenes: Application to thorium-uranyl separation in an actual sample.

Two novel extraction chromatography resins (ECRs) containing two diglycolamide (DGA) -functionalized calix[4]arenes with n-propyl and isopentyl substituents at the amide nitrogen atom, termed as ECR-1 and ECR-2, respectively, were evaluated for the uptake of Th(IV) from nitric acid feed solutions. While both the resins were having a quite high Th(IV) uptake ability (Kd >3000 at 3 M HNO3), the uptake was relatively lower with the resin containing the isopentyl DGA, which appeared magnified at lower nitric acid concentrations. Kinetic modeling of the sorption data suggested fitting to the pseudo-second order model pointing to a chemical reaction during the uptake of the metal ion. Sorption isotherm studies were carried out showing a good fitting to the Langmuir and D-R isotherm models, suggesting the uptake conforming to monolayer sorption and a chemisorption model. Glass columns with a bed volume of ca. 2.5 mL containing ca. 0.5 g lots of the ECRs were used for studies to assess the possibility of actual applications of the ECRs. Breakthrough profiles obtained with feed containing 0.7 g/L Th(NO3)3 solution resulted in breakthrough volumes of 8 and 5 mL, respectively, for the ECR-1 and ECR-2 resins. Near quantitative elution of the loaded metal ion was possible using a solution of oxalic acid and nitric acid. A method for the separation of Th-234 from natural uranium was demonstrated for the possible application of ECR-1.

Underwater detection of tonal signals between 0.125 and 100 kHz by harbor seals (Phoca vitulina).

The underwater hearing sensitivities of two 1-year-old female harbor seals were quantified in a pool built for acoustic research, using a behavioral psychoacoustic technique. The animals were trained to respond when they detected an acoustic signal and not to respond when they did not (go/no-go response). Pure tones (0.125-0.25 kHz) and narrowband frequency modulated (tonal) signals (center frequencies 0.5-100 kHz) of 900 ms duration were tested. Thresholds at each frequency were measured using the up-down staircase method and defined as the stimulus level resulting in a 50% detection rate. The audiograms of the two seals did not differ statistically: both plots showed the typical mammalian U-shape, but with a wide and flat bottom. Maximum sensitivity (54 dB re 1 microPa, rms) occurred at 1 kHz. The frequency range of best hearing (within 10 dB of maximum sensitivity) was from 0.5 to 40 kHz (6(1/3) octaves). Higher hearing thresholds (indicating poorer sensitivity) were observed below 1 and above 40 kHz. Thresholds below 4 kHz were lower than those previously described for harbor seals, which demonstrates the importance of using quiet facilities, built specifically for acoustic research, for hearing studies in marine mammals. The results suggest that under unmasked conditions many anthropogenic noise sources and sounds from conspecifics are audible to harbor seals at greater ranges than formerly believed.

Startle response of captive North Sea fish species to underwater tones between 0.1 and 64 kHz.

World-wide, underwater background noise levels are increasing due to anthropogenic activities. Little is known about the effects of anthropogenic noise on marine fish, and information is needed to predict any negative effects. Behavioural startle response thresholds were determined for eight marine fish species, held in a large tank, to tones of 0.1-64 kHz. Response threshold levels varied per frequency within and between species. For sea bass, the 50% reaction threshold occurred for signals of 0.1-0.7 kHz, for thicklip mullet 0.4-0.7 kHz, for pout 0.1-0.25 kHz, for horse mackerel 0.1-2 kHz and for Atlantic herring 4 kHz. For cod, pollack and eel, no 50% reaction thresholds were reached. Reaction threshold levels increased from approximately 100 dB (re 1 microPa, rms) at 0.1 kHz to approximately 160 dB at 0.7 kHz. The 50% reaction thresholds did not run parallel to the hearing curves. This shows that fish species react very differently to sound, and that generalisations about the effects of sound on fish should be made with care. As well as on the spectrum and level of anthropogenic sounds, the reactions of fish probably depend on the context (e.g. location, temperature, physiological state, age, body size, and school size).

Deterring effects of 8-45 kHz tone pulses on harbour seals (Phoca vitulina) in a large pool.

The marine aquaculture industry suffers losses due to pinniped attacks which damage net enclosures and fish stocks. Acoustic harassment devices (AHDs) emit loud sounds which are intended to deter pinnipeds from approaching aquaculture enclosures. At present, many AHDs emit sounds in the 8-20 kHz frequency range. It is not known whether sounds of higher frequencies have a deterrent effect on seals. Therefore five captive harbour seals (Phoca vitulina) were subjected to four series of tone pulses together spanning a broad frequency range (8, 16, 32 and 45 kHz). Pulse duration was 250 ms and pulse interval was 5s. Each of the four sounds was made deterrent by increasing the amplitude. The seals reacted by swimming away from the sounds. The displacement effect of each sound was judged by comparing the animals' surface positions, and number of surfacings, during ten 45 min baseline periods with ten 45 min test periods per frequency (one frequency per day in rotation, 40 sessions in total). The seals were displaced by all four frequencies throughout the 40 trial days. The seals came to the surface more often when the test tones were produced than in the baseline periods. The initial displacement distances did not change over the 40 test days. This suggests that operating AHDs for only short periods will be more effective and less likely to result in habituation by the seals than operating them continuously. The discomfort threshold sound pressure level (SPL) was established for each of the four pulse frequencies. The acoustic discomfort threshold SPL is defined as the boundary SPL between the area that the animals generally occupied during the transmission of the sounds and the area that they generally did not enter during sound transmission. The discomfort threshold SPL may depend on the context.

Receiving beam patterns in the horizontal plane of a harbor porpoise (Phocoena phocoena).

Receiving beam patterns of a harbor porpoise were measured in the horizontal plane, using narrow-band frequency modulated signals with center frequencies of 16, 64, and 100 kHz. Total signal duration was 1000 ms, including a 200 ms rise time and 300 ms fall time. The harbor porpoise was trained to participate in a psychophysical test and stationed itself horizontally in a specific direction in the center of a 16-m-diameter circle consisting of 16 equally-spaced underwater transducers. The animal's head and the transducers were in the same horizontal plane, 1.5 m below the water surface. The go/no-go response paradigm was used; the animal left the listening station when it heard a sound signal. The method of constants was applied. For each transducer the 50% detection threshold amplitude was determined in 16 trials per amplitude, for each of the three frequencies. The beam patterns were not symmetrical with respect to the midline of the animal's body, but had a deflection of 3-7 degrees to the right. The receiving beam pattern narrowed with increasing frequency. Assuming that the pattern is rotation-symmetrical according to an average of the horizontal beam pattern halves, the receiving directivity indices are 4.3 at 16 kHz, 6.0 at 64 kHz, and 11.7 dB at 100 kHz. The receiving directivity indices of the porpoise were lower than those measured for bottlenose dolphins. This means that harbor porpoises have wider receiving beam patterns than bottlenose dolphins for the same frequencies. Directivity of hearing improves the signal-to-noise ratio and thus is a tool for a better detection of certain signals in a given ambient noise condition.

Selective extraction of naturally occurring radioactive Ra2+.

Organic extractants play a significant role in the selective removal of radioactive cations from waste streams. Although, literature on the selective removal of man-made radioactive material such as Americium (Am) is widespread, the selective removal of naturally occurring radioactive material such as Ra2+ is only mentioned sporadically. This tutorial review deals with the selective extraction of the highly radiotoxic Ra2+. Special attention is paid to different types of organic extractants used.