Trophic structures of artificial reef communities off the southern coast of the Korean peninsula as determined using stable isotope analyses.

The deployment of artificial reefs (ARs) has become a popular technique for creating new hard-bottom habitats, and for enhancing biodiversity and resource abundance for fisheries. We compared colonizing faunal assemblages and reef-associated food-web structures between ARs and nearby natural reefs (NRs) off the Korean coast using stable isotope techniques. Reef communities showed high compositional disparities in colonizing assemblages. Distinct δ13C and δ15N ranges of functional groups could be used to distinguish pelagic from benthic trophic pathways in the reef food web. The isotopic niches of entire faunal assemblages, as well as individual functional groups, overlapped between NRs and ARs, resulting in equivalency for the isotopic functional indices. Mixing model estimates for carnivorous invertebrates and fish suggested strong trophic links to reef-associated faunal prey at both reef types. Finally, these results highlight a convergence in trophic structure between ARs and NRs in accordance with functional diversity in the colonized faunal assemblages.

Bioconcentration and distribution of silver nanoparticles in Japanese medaka (Oryzias latipes).

The study of the bioconcentration of silver nanoparticles (AgNPs) is important to fully understand their hazard potential in the aquatic environment. We synthesized AgNPs radiolabeled with silver isotopes ((110m)Ag) to quantify the bioconcentration of AgNPs coated with citrate (AgNPs-CIT) and polyvinylpyrrolidone (AgNPs-PVP) in Japanese medaka, and to investigate the biodistribution of silver in organs, which were compared with (110m)AgNO3. BCF values were determined to be 39.8±7.4, 42.5±5.1 and 116.4±6.1Lkg(-1) for AgNPs-CIT, AgNPs-PVP and AgNO3, respectively. The release of more silver ions in AgNPs-PVP contributed to a different kinetic uptake pattern with AgNPs-CIT, which was similar to that of AgNO3. Bioconcentrated AgNPs in medaka were not observed to be eliminated, independent of surface coating differences, similarly to AgNO3. There was no difference in biodistribution in each organ before and after depuration in two types of AgNPs and AgNO3, all of which were mainly concentrated in the liver. This study quantified the bioconcentration and distribution of AgNPs and AgNO3 more precisely by utilizing a silver isotope, which is helpful in monitoring the toxicity of AgNPs to Japanese medaka.

Effects of phytoplankton cell size and chloride concentration on the bioaccumulation of methylmercury in marine phytoplankton.

In the current study, the effects of phytoplankton cell size and methylmercury (MeHg) speciation on the bioaccumulation of MeHg by marine phytoplankton were investigated. Volume concentration factors (VCFs) of MeHg were determined in relation to the surface area to volume ratio of the cells for four species of diatom and a cyanobacteria species cultured in unenriched seawater. The VCFs of MeHg, ranging from 7.3 × 10(4) to 1.6 × 10(6) , increased linearly as the cell surface area-to-volume ratio increased. It suggests that pico- and nano-dominated phytoplankton communities may lead to larger MeHg accumulation than the one dominated by microphytoplankton. MeHg VCFs increased with increasing chloride concentration from 0.47 to 470 mM, indicating that MeHg bioaccumulation is enhanced under conditions that facilitate membrane permeability by the formation of neutral MeHgCl species. Overall results suggest that the size distributions of the planktonic community as well as the seawater chemistry affect MeHg bioaccumulation by marine phytoplankton.

Microbial synthesis of silver nanoparticles.

The objectives of this research were to study biogenic synthesis of Ag(0) nanoparticles and to determine the effects of various experimental conditions such as silver nitrate concentrations, pHs and temperatures controlling for the optimal biosynthesis of Ag(0) nanoparticles. The metal-reducing bacteria formed 5-15 nm-sized Ag(0) nanoparticles by reduction of 0.5-1 mM silver nitrate under the conditions around 15-25 degrees C and medium pH 7.5-8.5 within 3 days of incubation. These results not only show that the bacteria enzymatically reduced Ag(I), but also offer methods for microbial synthesis of homogeneous silver nanoparticles and silver recovery from the natural environments.

Facile synthesis and characterization of silver nanoparticle/bis(o-phenolpropyl)silicone composites using a gold catalyst.

The generation of silver nanoparticle/bis(o-phenolpropyl)silicone composites have been facilitated by the addition of sodium tetrachloroaurate or gold(Ill) chloride (< 1 wt% of NaAuCl4 or AuCl3) to the reaction of silver nitrate (AgNO3) with bis(o-phenolpropyl)silicone [BPPS, (o-phenolpropyl)2(SiMe2O)n, n = 2,3,8,236]. TEM and FE-SEM data showed that the silver nanoparticles having the size of < 20 nm are well dispersed throughout the BPPS silicone matrix in the composites. XRD patterns are consistent with those for polycrystalline silver. The size of silver nanoparticles augmented with increasing the relative molar concentration of AgNO3 added with respect to BPPS. The addition of gold complexes (1-3 wt%) did not affect the size distribution of silver nanoparticles appreciably. In the absence of BPPS, the macroscopic precipitation of silver by agglomeration, indicating that BPPS is necessary to stabilize the silver nanoparticles surrounded by coordination.

Synthesis and characterization of silver nanoparticle composite with poly(p-Br-phenylsilane).

The one-pot synthesis and characterization of silver nanoparticle-poly(p-Br-phenylsilane) composites have been carried out. The conversion of silver(+1) salt to stable silver(0) nanoparticles is promoted by poly(p-Br-phenylsilane), Br-PPS possessing both possible reactive Si-H bonds in the polymer backbone and C-Br bonds in the substituents. The composites were characterized using XRD, TEM, FE-SEM, and solid-state UV-vis analytical techniques. TEM and FE-SEM data show the formation of the composites where large number of silver nanoparticles (less than 30 nm of size) are well dispersed throughout the Br-PPS matrix. XRD patterns are consistent with that for fcc-typed silver. The elemental analysis for Br atom and the polymer solubility confirm that the cleavage of C-Br bond and the Si-Br dative bonding were not occurred appreciably at ambient temperature. Nonetheless, TGA data suggest that some sort of cross-linking was occurred at high temperature. The size and processability of such nanoparticles depend on the ratio of metal to Br-PPS. In the absence of Br-PPS, most of the silver particles undergo macroscopic aggregation, which indicates that the polysilane is necessary for stabilizing the silver nanoparticles.

Embryonic toxicity changes of organic nanomaterials in the presence of natural organic matter.

When elucidating the potential fate and bioavailability of nanomaterials (NMs) in an aquatic system, it is important to consider the interactions between NMs and natural organic matter (NOM). The present study compared the toxicities of carbon-based NMs, with disparate physicochemical properties, on Japanese medaka (Oryzias latipes) embryos after the addition of NOM. The measured embryonic toxicity parameters were mortality, malformation and hatching delay. Various physicochemical properties of water suspended fullerenes (nC(60)) and multi-walled carbon nanotubes (MWNTs) were modulated by organic exchange (Tol/nC(60)), stirring over time (Aqu/nC(60)) and acid treatment (f-MWNTs) followed by characterization. Tol/nC(60) produced relatively more hydrophobic surfaces and exhibited smaller closed spherical agglomerates than Aqu/nC(60). Acid-treated f-MWNTs displayed functionalized hydrophilic surfaces compared to raw MWNTs (r-MWNTs). The resultant embryonic toxicities, in the absence of NOM, were ranked in the order: f-MWNTs>Tol/nC(60)>Aqu/nC(60). As the NOM concentrations were increased, no changes in embryonic toxicities were observed on exposure of Aqu/nC(60) and r-MWNTs; whereas, the toxicities were reduced on exposure to Tol/nC(60) and f-MWNTs, due to a disappearance of hydrophobic primary spherical aggregates and partial coating, respectively. These data suggest that in the presence of NOM, the morphological differences of NMs, as well as their physicochemical properties, play a significant role in their reactions and subsequent medaka embryonic nanotoxicity.

Biomagnification of mercury through the benthic food webs of a temperate estuary: Masan Bay, Korea.

The authors examined food web magnification factors of total mercury (THg) and methylmercury (MeHg) for the benthic organisms in Masan Bay, a semiclosed, temperate estuary located on the southeastern coast of Korea. For benthic invertebrates, concentrations of THg and MeHg (%MeHg) ranged from 9.57 to 195 and 2.56 to 111 ng/g dry weight (12.2-85.6%), respectively. Benthic fish THg and MeHg (%MeHg) concentrations ranged widely from 10.8 to 618 and 2.90 to 529 ng/g dry weight (22.9-93.9%), respectively. The linear regression slopes of log [Hg] relative to δ(15)N (i.e., food web magnification factors) found for the Masan Bay benthic organisms were 0.119 for THg and 0.168 for MeHg. These values are similar to the food web magnification factors of benthic organisms and lower than those of pelagic organisms of various coastal marine environments. It suggests that pelagic organisms might be at greater risk of THg and MeHg accumulation than benthic biota.

Rapid synthesis and characterization of silver nanoparticle/bis(o-phenolpropyl)silicone composites by platinum.

The formation of silver nanoparticle/bis(o-phenolpropyl)silicone composites have been promoted by the addition of chloroplatinic acid (<2 wt%) to the reaction of silver nitrate with bis(o-phenolpropyl)silicone BPPS [(o-phenolpropyl)2(SiMe2O)n, = 2, 3, 8, 236]. TEM and FE-SEM data exhibit that the silver nanoparticles having the size of <20 nm are well dispersed throughout the BPPS matrix in the composites. XRD patterns are consistent with those for polycrystalline silver. The addition of small amount of platinum to the silver accelerated the rate of composite formation by forming a Ag-Pt bimetallic alloy. The size of silver nanoparticles increased with increasing the relative molar concentration of silver salts added with respect to BPPS. However, the addition of platinum (1-5 wt%) to the AgNO3-BPPS mixture did not affect the size distribution of silver nanoparticles appreciably. It was found that in the absence of BPPS, most of the silver nanoparticles undergo macroscopic precipitation by agglomeration, indicating that BPPS is essential to stabilize the silver nanoparticles by coordination.

Efficient synthesis and structural characterization of silver nanoparticle/ bis(o-phenolpropyl)silicone composites.

Silver nanoparticle/bis(o-phenolpropyl)silicone composites have been synthesized by the reduction of silver nitrate with bis(o-phenolpropyl)silicone BPPS [(o-phenolpropyl)2(SiMe2O)n, n = 2, 3, 8, 236]. TEM and FE-SEM data clearly show that the silver nanoparticles with the size of < 20 nm are well dispersed throughout the BPPS matrix in the composites. XRD patterns are consistent with those for multicrystalline silver. The size of silver nanoparticles increased with increasing the relative molar concentration of silver salts added. It was found that in the absence of BPPS, most of the silver nanoparticles undergo macroscopic precipitation by agglomeration, indicating that BPPS is essential to stabilize the silver nanoparticles.

Efficient preparation and characterization of silver-polyphenylsilane nanocomposites.

Silver-polyphenylsilane nanocomposites have been effectively prepared by the dehydrocoupling reaction of phenylsilane (PS, PhSiH3) to polyphenylsilane (PPS, [PhSiH]n) in the presence of silver nitrate. The one-step reduction of Ag(+1) nitrate to stable Ag(0) nanoparticles is mediated by PS, resulting in the formation of Ag-PPS composites. The Ag-PPS nanocomposites were characterized by various analytical techniques such as XRD, TEM, FE-SEM, and solid-state UV-vis. TEM and FE-SEM data clearly show that the silver nanoparticles with the size of < 20 nm are well dispersed throughout the PPS matrix in the nanocomposites. XRD patterns are consistent with those for fcc crystalline silver. The size of silver nanoparticles increased with increasing the relative molar concentration of silver salts added. It was found that in the absence of PS, most of the silver nanoparticles undergo macroscopic precipitation by aggregation, indicating that PPS is essential to stabilize the silver nanoparticles by the complexation of Si-H to the silver metal centers.

Catalytic sol-gel co-polycondensation of para-substituted phenylsilanes and bis(silyl)phenylene to robust organosilicas using colloidal nickel nanoparticles.

The dry sol-gel co-polycondensation at toluene in ambient air atmosphere of p-X-C6H4SiH3 (X = H, CH3, CH3O, F, Cl) and p-H3Si-C6H4SiH3 (9:1 mole ratio) to co-silicas (p-X-C6H4SiO1.5)9(p-O1.5Si-C6H4SiO1.5)1 in high yield, catalyzed by colloidal nickel nanoparticles in-situ generated from nickelocene(II) is described. The co-gels (p-X-C6H4SiO1.5)9(p-O1.5Si-C6H4SiO1.5)1 with higher molecular weights and TGA residue yield were obtained when compared to the homogels p-X-C6H4SiO1.5 Some degree of unreacted Si-H bonds still remained in the gel matrix because of steric bulkiness. All the insoluble gels adopt an amorphous structure with a smooth surface. A plausible mechanism for the dry sol-gel reaction was provided.

Importance of equilibration time in the partitioning and toxicity of zinc in spiked sediment bioassays.

The influences of spiked Zn concentrations (1-40 micromol/g) and equilibration time (approximately 95 d) on the partitioning of Zn between pore water (PW) and sediment were evaluated with estuarine sediments containing two levels (5 and 15 micromol/g) of acid volatile sulfides (AVS). Their influence on Zn bioavailability was also evaluated by a parallel, 10-d amphipod (Leptocheirus plumulosus) mortality test at 5, 20, and 85 d of equilibration. During the equilibration, AVS increased (up to twofold) with spiked Zn concentration ([Zn]), whereas Zn-simultaneously extracted metals ([SEM]; Zn with AVS) remained relatively constant. Concentrations of Zn in PW decreased most rapidly during the initial 30 d and by 11- to 23-fold during the whole 95-d equilibration period. The apparent partitioning coefficient (Kpw, ratio of [Zn] in SEM to PW) increased by 10- to 20-fold with time and decreased with spiked [Zn] in sediments. The decrease of PW [Zn] could be explained by a combination of changes in AVS and redistribution of Zn into more insoluble phases as the sediment aged. Amphipod mortality decreased significantly with the equilibration time, consistent with decrease in dissolved [Zn]. The median lethal concentration (LC50) value (33 microM) in the second bioassay, conducted after 20 d of equilibration, was twofold the LC50 in the initial bioassay at 5 d of equilibration, probably because of the change of dissolved Zn speciation. Sediment bioassay protocols employing a short equilibration time and high spiked metal concentrations could accentuate partitioning of metals to the dissolved phase and shift the pathway for metal exposure toward the dissolved phase.