Phytoplankton assemblage responses to massive freshwater inputs and anthropogenic toxic substances contamination in the Geum River Estuary, South Korea.

This study investigated the relationships between phytoplankton assemblages and water contamination by persistent toxic substances (PTSs) and nutrients in an estuary with an artificial dam over one year. The distribution of PTSs, including 15 polycyclic aromatic hydrocarbons, 6 alkylphenols, and 8 metal(loid)s, along with nutrients, exhibited relatively high concentrations with irregular temporal fluctuations in the inner estuary. During winter and spring, phytoplankton communities showed good ecological quality, with an average of 28 species and a density of 1750 cells L-1. In contrast, during summer, there was a significant increase in the density of freshwater species (max 45,000 cells L-1). These assemblages were categorized into three seasonal groups, featuring dominant taxa like blue-green algae and diatoms. Temperature and nutrient levels were the principal factors influencing phytoplankton assemblages, while PTSs had a minor impact. Overall, phytoplankton assemblages displayed strong seasonal variation, mainly influenced by freshwater input and nutrient availability.

Facile Transfer of Spray-Coated Ultrathin AgNWs Composite onto the Skin for Electrophysiological Sensors.

Disposable wearable sensors that ultrathin and conformable to the skin are of significant interest as affordable and easy-to-use devices for short-term recording. This study presents a facile and low-cost method for transferring spray-coated silver nanowire (AgNW) composite films onto human skin using glossy paper (GP) and liquid bandages (LB). Due to the moderately hydrophobic and rough surface of the GP, the ultrathin AgNWs composite film (~200 nm) was easily transferred onto human skin. The AgNW composite films conformally attached to the skin when applied with a LB, resulting in the stable and continuous recording of wearable electrophysiological signals, including electromyogram (EMG), electrocardiogram (ECG), and electrooculogram (EOG). The volatile LB, deposited on the skin via spray coating, promoted rapid adhesion of the transferred AgNW composite films, ensuring stability to the AgNWs in external environments. The AgNWs composite supported with the LB film exhibited high water vapor breathability (~28 gm-2h-1), which can avoid the accumulation of sweat at the skin-sensor interface. This approach facilitates the creation of rapid, low-cost, and disposable tattoo-like sensors that are practical for extended use.

Association between Mild Cognitive Impairment and Gut Microbiota in Elderly Korean Patients.

Recent studies have confirmed that gut microbiota differs according to race or country in many diseases, including mild cognitive impairment (MCI) and Alzheimer's disease. However, no study has analyzed the characteristics of Korean MCI patients. This study was performed to observe the association between gut microbiota and MCI in the Korean elderly and to identify potential markers for Korean MCI patients. For this purpose, we collected fecal samples from Korean subjects who were divided into an MCI group (n = 40) and control group (n = 40) for 16S rRNA gene amplicon sequencing. Although no significant difference was observed in the overall microbial community profile, the relative abundance of several genera, including Bacteroides, Prevotella, and Akkermansia, showed significant differences between the two groups. In addition, the relative abundance of Prevotella was negatively correlated with that of Bacteroides (r = 0.733). This study may provide Korean-specific basic data for comparing the characteristics of the gut microbiota between Korean and non-Korean MCI patients.

Current Situation of Palytoxins and Cyclic Imines in Asia-Pacific Countries: Causative Phytoplankton Species and Seafood Poisoning.

Among marine biotoxins, palytoxins (PlTXs) and cyclic imines (CIs), including spirolides, pinnatoxins, pteriatoxins, and gymnodimines, are not managed in many countries, such as the USA, European nations, and South Korea, because there are not enough poisoning cases or data for the limits on these biotoxins. In this article, we review unregulated marine biotoxins (e.g., PlTXs and CIs), their toxicity, causative phytoplankton species, and toxin extraction and detection protocols. Due to global warming, the habitat of the causative phytoplankton has expanded to the Asia-Pacific region. When ingested by humans, shellfish that accumulated toxins can cause various symptoms (muscle pain or diarrhea) and even death. There are no systematic reports on the occurrence of these toxins; however, it is important to continuously monitor causative phytoplankton and poisoning of accumulating shellfish by PlTXs and CI toxins because of the high risk of toxicity in human consumers.

Distribution of microcystins in environmental multimedia and their bioaccumulation characteristics in marine benthic organisms in the Geum River Estuary, South Korea.

Spatio-temporal distributions and bioaccumulation characteristics of freshwater cyanobacterial toxins, such as microcystins (MCs) in the Geum River Estuary, South Korea, were investigated during summer. Environmental multimedia samples (water, suspended particulate matter (SPM), and sediments) and tidal flat organisms (polychaetes, decapods, amphipods, and bivalves) were collected from regions inside and outside of the estuary dam for MCs analysis. Phytoplankton communities in the Geum River (freshwater) and estuarine area (brackish water) were also analyzed in order to understand the relationship with MCs concentrations. Seasonal variation in the structure of phytoplankton communities was detected in the Geum River, with a relatively high density of Cyanophyta in summer. MC concentrations were strongly correlated to water temperature, chlorophyll a, and cyanobacterial density. MC-LR was the most abundant MC variants in environmental samples. Dissolved MCs remained for longer periods and were more widely distributed in the coastal environments compared to particulate MCs. The distribution coefficients between water and SPM (Kd-SPM) and between water and sediments (Kd-sediment) of MCs showed that the phase shift of MCs in the environmental samples occurred in the estuary. Kd-SPM declined from the inside to outside regions of the estuary dam, and was mainly attributed to differences in the half-lives of MCs in dissolved (4.7 d for MC-LR) and particulate phases (0.44-0.52 d for MC-LR). Species-specific bioaccumulation of MCs occurred in tidal flat organisms, with relatively high bioaccumulation factors of MCs being detected in polychaetes and decapods compared to amphipods and bivalves. Overall, this study advances our understanding on the distribution, transport, fate, and bioaccumulation of MCs in estuarine and coastal environments.

Macrozoobenthic community responses to sedimentary contaminations by anthropogenic toxic substances in the Geum River Estuary, South Korea.

We investigated the sedimentary pollution by persistent toxic substances (PTSs) and their potential impacts on the macrobenthic faunal community in the Geum River Estuary, South Korea. Sediment and benthic macrofauna samples were collected from eight sites every two months during the period of February to December in 2015. Target PTSs encompassed metals (Cd, Cr, Cu, Hg, Ni, Pb, and Zn), one metalloid (As), polycyclic aromatic hydrocarbons (PAHs), and alkylphenols (APs). The significant difference to the environment of the inner and outer parts of the estuary (p < 0.05) was found with relatively high concentrations of PTSs in sediment from the inner estuary. The concentrations of Cu and Zn exceeded the sediment quality guidelines of Korea representing a potential risk to aquatic organisms. The primary source of PAHs was by-products of diesel and gasoline combustion (37%), followed by a coke oven (32%) and oil-burning (31%). The macrofaunal community was spatially distinguished between the inner and outer parts of the estuary (p < 0.05), regardless of the season. In the inner part of the estuary, the density of the macrofaunal community was high, due to the increased opportunistic species and/or some indicator species (organic polluted or enrichment), implying that the given environment was disturbed. Among the environmental parameters analyzed by the distance-based linear model (DistLM), salinity, chlorophyll-a, and nutrient concentrations were found to be key factors controlling the changes in macrofaunal community structure. Such changes in the closed estuary system would indicate that each taxonomic group had to adjust to lower salinities and alternative food sources. Overall, the distribution of PTSs and macrozoobenthic communities in the Geum River Estuary collectively reflected the environmental gradients caused by surrounding activities in the inner part of the estuary together with direct effects by the irregular inflow of freshwater.

Multimedia distributions, bioaccumulation, and trophic transfer of microcystins in the Geum River Estuary, Korea: Application of compound-specific isotope analysis of amino acids.

To determine distributions, bioaccumulation, and trophic transfer of freshwater cyanobacterial toxins such as microcystins (MCs), surface water, suspended solids, sediments, and coastal organisms were collected from seven stations in inner and outer regions of the estuary dam in the Geum River Estuary in June and July 2017. Concentrations of MC variants (MC-LR, -RR, and -YR) in the multimedia samples were analyzed using a HPLC-MS/MS. Trophic position (TP) of organisms (fish, bivalve, gastropod, decapod, and polychaete) was determined by nitrogen stable isotope analyses of both bulk tissues and amino acids. From July to August 2017, great concentrations of MCs were detected in discharged freshwater ranging from 0.4 to 75 µg L-1. Considerable amounts of MCs are delivered to the Geum River Estuary in summer season. MCs spread far away as dissolved phases (18.7-49.5 ng L-1) in July when large amount of freshwater was discharged during the rainy season. Concentrations of MCs in marine organisms varied among species, ranging from 40 to 870 ng g-1 dw. Bioaccumulated MCs tend to decrease with increasing TP of organisms, suggesting that MCs are biodiluted through the marine food web. Compound-specific isotope analysis (nitrogen of amino acids) provides more reliable TPs compared with those by bulk isotope analysis in a closed estuary (such as the Geum River Estuary) with large fluctuations in the isotope ratio of primary producers.

Major AhR-active chemicals in sediments of Lake Sihwa, South Korea: Application of effect-directed analysis combined with full-scan screening analysis.

This study utilized effect-directed analysis (EDA) combined with full-scan screening analysis (FSA) to identify aryl hydrocarbon receptor (AhR)-active compounds in sediments of inland creeks flowing into Lake Sihwa, South Korea. The specific objectives were to (i) investigate the major AhR-active fractions of organic extracts of sediments by using H4IIE-luc in vitro bioassay (4 h and 72 h exposures), (ii) quantify known AhR agonists, such as polycyclic aromatic hydrocarbons (PAHs) and styrene oligomers (SOs), (iii) identify unknown AhR agonists by use of gas chromatography-quadrupole time-of-flight mass spectrometry (GC-QTOFMS), and (iv) determine contributions of AhR agonists to total potencies measured by use of the bioassay. FSA was conducted on fractions F2.6 and F2.7 (aromatics with log Kow 5-7) in extracts of sediment from Siheung Creek (industrial area). Those fractions exhibited significant AhR-mediated potency as well as relatively great concentrations of PAHs and SOs. FSA detected 461 and 449 compounds in F2.6 and F2.7, respectively. Of these, five tentative candidates of AhR agonist were selected based on NIST library matching, aromatic structures and numbers of rings, and available standards. Benz[b]anthracene, 11H-benzo[a]fluorene, and 4,5-methanochrysene exhibited significant AhR-mediated potency in the H4IIE-luc bioassay, and relative potencies of these compounds were determined. Potency balance analysis demonstrated that these three newly identified AhR agonists explained 1.1% to 67% of total induced AhR-mediated potencies of samples, which were particularly great for industrial sediments. Follow-up studies on sources and ecotoxicological effects of these compounds in coastal environments would be required.

Anthropogenic influences on benthic food web dynamics by interrupted freshwater discharge in a closed Geum River estuary, Korea.

Stable isotope analysis was used to investigate the benthic food web dynamics in the Geum River estuary where continuous river flow has been blocked by a sea dike over the past 25 years. In order to address the dike effect(s) on distribution of food sources (i.e., organic matters and microphytobenthos) and their utilization by marine predators, a three years monitoring survey (total of 30 surveys) was seasonally conducted at four fixed locations at both inside of dike and outer tidal flats. All the collected biota (total of 19 species; >1100 individuals and microphytobenthos) and abiotic (n = 118) samples were analyzed for carbon (δ13C) and nitrogen (δ15N) stable isotopes. In particular, two dominant marine bivalves inhabiting outer reach of tidal flats, Mactra veneriformis and Cyclina sinensis, were targeted to identify their feeding strategies that being related to a year-round population growth. In general, the stable isotopic signatures of samples indicated dissimilarity in distribution of organic matters between inside and outside of dike, supporting geographical and/or trophic isolation. The taxa-dependent trophic levels are also evidenced in consistent manner, with two to three levels being positioned over the years. Meantime, their dietary contributions varied in time, i.e., seasonal chances in compositions of major food sources (microphytobenthos and particulate organic matters) were observed for two target bivalves. Such temporal variations could be further linked to selective feedings that evidenced by age(size)-dependent and/or tissue specific distributions. Altogether, the present study suggested seasonality, diet preference, and growth dependent food web dynamics in the Geum River estuary. Overall, the present study suggested that the stable isotopic technique could be a powerful tool for characterizing the long-term anthropogenic influences of a sea dike on marine food-web dynamics.

Newly Identified AhR-Active Compounds in the Sediments of an Industrial Area Using Effect-Directed Analysis.

Effect-directed analysis was used to identify previously unidentified aryl hydrocarbon receptor (AhR) agonists in sediments collected from a highly industrialized area of Ulsan Bay, Korea. The specific objectives were to (i) investigate potent fractions of sediment extracts using the H4IIE-luc bioassay, (ii) determine the concentrations of known AhR agonists (polycyclic aromatic hydrocarbons (PAHs) and styrene oligomers (SOs)), (iii) identify previously unreported AhR agonists in fractions by use of GC-QTOFMS, and (iv) evaluate contributions of individual compounds to overall AhR-mediated potencies, found primarily in fractions containing aromatics with log Kow 5-8. Greater concentrations of PAHs and SOs were also found in those fractions. On the basis of GC-QTOFMS and GC-MSD analyses, 16 candidates for AhR agonists were identified in extracts of sediments. Of these, seven compounds, including 1-methylchrysene, benzo[j]fluoranthene, 3-methylchrysene, 5-methylbenz[a]anthracene, 11H-benzo[b]fluorene, benzo[b]naphtho[2,3-d]furan, and benzo[b]naphtho[2,1-d]thiophene, exhibited significant AhR activity. Relative potency values of newly identified AhR agonists were found to be greater than or comparable to that of benzo[a]pyrene (BaP). The potency balance analysis showed that newly identified AhR agonists explained 0.07-16% of bioassay-derived BaP-EQs. These chemicals were widely distributed in industrial sediments; thus, it is of immediate importance to conduct studies on sources and potential effects of those chemicals.

Using nanoscale thermocapillary flows to create arrays of purely semiconducting single-walled carbon nanotubes.

Among the remarkable variety of semiconducting nanomaterials that have been discovered over the past two decades, single-walled carbon nanotubes remain uniquely well suited for applications in high-performance electronics, sensors and other technologies. The most advanced opportunities demand the ability to form perfectly aligned, horizontal arrays of purely semiconducting, chemically pristine carbon nanotubes. Here, we present strategies that offer this capability. Nanoscale thermocapillary flows in thin-film organic coatings followed by reactive ion etching serve as highly efficient means for selectively removing metallic carbon nanotubes from electronically heterogeneous aligned arrays grown on quartz substrates. The low temperatures and unusual physics associated with this process enable robust, scalable operation, with clear potential for practical use. We carry out detailed experimental and theoretical studies to reveal all of the essential attributes of the underlying thermophysical phenomena. We demonstrate use of the purified arrays in transistors that achieve mobilities exceeding 1,000 cm(2) V(-1) s(-1) and on/off switching ratios of ∼10,000 with current outputs in the milliamp range. Simple logic gates built using such devices represent the first steps toward integration into more complex circuits.

Electrostatic dimension of aligned-array carbon nanotube field-effect transistors.

Accurate electrostatics modeling of nanotubes (NTs)/nanowires (NWs) has significant implications for the ultimate scalability of aligned-array NT/NW field-effect transistors (FETs). The analysis to date has focused on limits of capacitive coupling between the 1D channel and 2D gate that is strictly relevant only in the linear response operation of NT/NW-FETs. Moreover, the techniques of electrostatic doping by independent gates that cover only part of the channel are widely used, but the nature of its electrostatic coupling has not been explored. In this paper, we use a three-dimensional, self-consistent model for NT/NW-FETs to interpret the essence of electrostatic coupling with complex configuration of electrode geometries. The interplay between 3D electric fields and its 1D termination onto the NTs/NWs suggests surprising complexity of electrostatic interaction not captured in simpler models. This coupling can change the performance metrics such as ON and OFF currents by orders of magnitude depending on (1) NT/NW density, (2) bias voltage, and (3) gate overlap length. Remarkably, this parasitic coupling persists regardless of the gate oxide thickness, changes in dielectric constant, and/or the width of the diameter distribution of NTs/NWs. The predictions of the model are systematically validated by a series of experiments.

Low-temperature preparation of highly conductive thin films from acrylic acid-stabilized silver nanoparticles prepared through ligand exchange.

The preparation of AcA-stabilized Ag nanoparticles and its application to make highly conductive thin films are reported. The AcA-stabilized Ag nanoparticles were prepared through a ligand exchange of original oleylamine (OLA)-coated Ag nanoparticles with acrylic acid (AcA), which acted as both an antisolvent and a modifying ligand during the ligand exchange process. Efficiencies of the ligand exchange as well as the properties of Ag nanoparticles were analyzed using various techniques including TEM, FT-IR, XPS, TGA, and UV-vis methods. The thin films were fabricated by annealing spin-coated AcA-stabilized Ag nanoparticles. Further, the effects of annealing temperature, time, and film thickness on both the film morphology and electrical conductivity have been investigated. In this work, due to the low boiling temperature of stabilizer (AcA) and adjustment of annealing conditions, high electrical conductivity was obtained for the Ag thin films. For example, when annealing at 175 °C for 30 min, a 70 nm thick film showed a maximum electrical conductivity of 1.12 × 10(5) S cm(-1). A conductive layer on a flexible polymer substrate (e.g., PET) sheet has been successfully prepared by annealing a spin-coated film at 140 °C for 30 min. The combined advantages of long-term stability of the AcA-stabilized Ag nanoparticles, low annealing temperature, and high conductivity of the prepared thin films make this relatively simple method attractive for applications in flexible electronics.