Vibrational predissociation spectra of protonated water clusters H+(H2O)n, n = 9-11, are presented. Examination of the spectra in the free-OH stretching region revealed predominance of a single absorption band at approximately 3690 cm(-1) for three-coordinate H2O acting as a double-proton-acceptor/single-proton-donor in the n = 11 cluster. In contrast, the intensity of the absorption band of two-coordinate H2O acting as a single-proton-acceptor/single-proton-donor at approximately 3715 cm(-1) decreases with cluster size, and that of one-coordinate H2O acting as a single-proton-acceptor at approximately 3740 and approximately 3650 cm(-1) diminishes nearly entirely at n > 10 in the spectrum. To deduce the information about cluster temperature, we measured the spontaneous dissociation rates of the cluster ions inside an octopole ion trap and fitted the measured rate constants to an empirical Arrhenius equation. Temperatures in the range of 150 K were estimated for all H+ (H2O)9-11, suggesting that the thermal effect may populate the structures other than the true ground state. The results, combined with previously acquired spectra for H+ (H2O)5-8 (J.-C. Jiang, Y.-S. Wang, H.-C. Chang, S. H. Lin, Y. T. Lee, G. Niedner-Schatteburg and H.-C. Chang, J. Am. Chem. Soc., 2000, 122, 1398) and Monte Carlo simulations with the OSS2 model potential (L. Ojamlie, I. Shavitt and S. J. Singer, J. Chem. Phys., 1998, 109, 5547), show a systematic change in hydrogen-bond topology from tree-like, single-ring, multiple-ring to cage-like isomers (and their mixtures) as the cluster size increases from n = 5 to n = 11.
This paper describes a systematic study on the clathrate structure of (H+)(H2O)21 using tandem mass spectrometry, vibrational predissociation spectroscopy, Monte Carlo simulations, and density functional theory calculations. We produced (H+)(H2O)n from a continuous corona-discharged supersonic expansion and observed three anomalies simultaneously at the cluster temperature near 150 K, including (1) the peak at n=21 is more intense than its neighboring ions in the mass spectrum, (2) the size-dependent dissociation fractions show a distinct drop for the 21-mer, and (3) the infrared spectrum of (H+)(H2O)21 exhibits only a single feature at 3699 cm(-1), corresponding to the free-OH stretching of three-coordinated water molecules. Interestingly, the anomalies appear or disappear together with cluster temperature, indicating close correlation of these three observations. The observations, together with Monte Carlo simulations and density functional theory calculations, corroborate the notion for the formation of a distorted pentagonal dodecahedral (5(12)) cage with a H2O molecule in the cage and a H3O+ ion on the surface for this "magic number" water cluster ion. The dodecahedral cage melts at higher temperatures, as evidenced by the emergence of a free-OH stretching feature at 3717 cm(-1) for the two-coordinated water in (H+)(H2O)21 produced in a warmer molecular beam. Extension of this study to larger clusters strongly suggests that the experimentally observed isomer of (H+)(H2O)28 is most likely to consist of a distorted protonated pentakaidecahedral (5(12)6(3)) cage enclosing two neutral water molecules.
Coastal aquaculture in Bangladesh consists mainly of two shrimp species (Penaeus monodon and Macrobrachium rosenbergii). Currently, there are about 16,237 marine shrimp (P. monodon) farms covering 148,093 ha and 36,109 fresh water shrimp (M. rosenbergii) farms covering 17,638 ha coastal area. More than 0.7 million people are employed in the farmed shrimp sector and in 2005-2006 the export value of shrimp was 403.5 million USD. Thus, coastal aquaculture contributes significantly to rural employment and economy but this is overshadowed by negative social and ecological impacts. This article reviews the key issues, constraints and opportunities of sustainable shrimp farming. In addition we present the results of two case studies from southwestern coastal areas where shrimp farming originated and central coastal areas where shrimp farming, especially M. rosenbergii, began in recent years. Lessons learned from the review and case studies are considered in the context of recommendations to encompass a socially equitable and ecologically sound coastal aquaculture.
The addition of feed to fertilized fish ponds was evaluated by adding feed alone, feed plus fertilizer, or fertilizer alone to nine ponds stocked with Nile tilapia Oreochromis niloticus. Two experiments were conducted. The first had 500 fish per 250 m2 pond in 3 treatments: ad‐libitum feeding; fertilizer only; or fertilizer and ad‐libitum feeding. The second experiment had 5 treatments with 750 fish per pond ad‐libitum feed only; fertilizer only; or 0.25, 0.50, and 0.75 satiation ration plus fertilizer. Ponds in Thailand were maintained for 155–162 d, during which chemical and physical properties were monitored. In experiment 1 tilapia growth was highest in feed only ponds, and lowest in fertilizer only ponds. Net yield did not differ significantly among treatments, due to variation in survival. In experiment 2, tilapia growth was lowest in fertilizer only ponds, intermediate in 0.25 ration ponds, and highest in 0.50, 0.75, and ad‐libitum ponds. The latter treatments were not significantly different. Multiple regressions for each experiment indicated only 47–87% of the variance in growth was explained by feed and fertilizer input, while 52–89% of the variance in yield was explained by those factors. For both experiments combined, 90.3% of the variance in growth was explained by feed input, fertilizer input, alkalinity, and total inorganic nitrogen concentration. For yield, R2 was 0.888 and the regression included feed input, pH, and number of low dissolved oxygen events. Experiment 1 appeared to approach carrying capacity near the end, while no reduction in growth occurred in experiment 2 at higher fish density and biomass. Reductions in growth in experiment 1 were not correlated with declining water quality late in the grow out. Combinations of feed and fertilizer were most efficient in growing tilapia to large size (500 g) compared to complete feeding or fertilizing alone.
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