Recent Trends in Chemical Sensors for Detecting Toxic Materials.

Industrial development has led to the widespread production of toxic materials, including carcinogenic, mutagenic, and toxic chemicals. Even with strict management and control measures, such materials still pose threats to human health. Therefore, convenient chemical sensors are required for toxic chemical monitoring, such as optical, electrochemical, nanomaterial-based, and biological-system-based sensors. Many existing and new chemical sensors have been developed, as well as new methods based on novel technologies for detecting toxic materials. The emergence of material sciences and advanced technologies for fabrication and signal-transducing processes has led to substantial improvements in the sensing elements for target recognition and signal-transducing elements for reporting interactions between targets and sensing elements. Many excellent reviews have effectively summarized the general principles and applications of different types of chemical sensors. Therefore, this review focuses on chemical sensor advancements in terms of the sensing and signal-transducing elements, as well as more recent achievements in chemical sensors for toxic material detection. We also discuss recent trends in biosensors for the detection of toxic materials.

The Biomedical Applications of Biomolecule Integrated Biosensors for Cell Monitoring.

Cell monitoring is essential for understanding the physiological conditions and cell abnormalities induced by various stimuli, such as stress factors, microbial invasion, and diseases. Currently, various techniques for detecting cell abnormalities and metabolites originating from specific cells are employed to obtain information on cells in terms of human health. Although the states of cells have traditionally been accessed using instrument-based analysis, this has been replaced by various sensor systems equipped with new materials and technologies. Various sensor systems have been developed for monitoring cells by recognizing biological markers such as proteins on cell surfaces, components on plasma membranes, secreted metabolites, and DNA sequences. Sensor systems are classified into subclasses, such as chemical sensors and biosensors, based on the components used to recognize the targets. In this review, we aim to outline the fundamental principles of sensor systems used for monitoring cells, encompassing both biosensors and chemical sensors. Specifically, we focus on biosensing systems in terms of the types of sensing and signal-transducing elements and introduce recent advancements and applications of biosensors. Finally, we address the present challenges in biosensor systems and the prospects that should be considered to enhance biosensor performance. Although this review covers the application of biosensors for monitoring cells, we believe that it can provide valuable insights for researchers and general readers interested in the advancements of biosensing and its further applications in biomedical fields.

Role of Algal Community Stability in Harmful Algal Blooms in River-Connected Lakes.

Harmful algal blooms (HABs) in freshwater produce toxins that pose a threat to public health and aquatic ecosystems. Although algal communities have been studied globally to understand the characteristics of HABs, the occurrence of toxic cyanobacteria in freshwater ecosystems is rarely understood. Unlike abiotic factors, the effects of biotic factors (e.g., interaction, dominance, and variability) on the occurrence of toxic cyanobacteria were overlooked due to the intricate interaction of microorganisms under different environmental conditions. To address this problem, a comprehensive ecological concept stability, which encompasses variations in species or communities due to changing biological interactions or environmental fluctuations, was applied in this study. The algal communities in six river-connected lakes in the North Han River, South Korea, were classified into high and low stability groups. The algal species belonging to diatoms and green algae groups played a major role in the interaction within the algal community in highly stable lakes, but the frequency of Microcystis led the interaction within the algal community at the center of the network in low-stability lakes. These results indicate that the interaction within the cluster is easily changed by Microcystis, where the abundance explosively increases in lakes with low algal community stability. Water quality is more strongly associated with the occurrence of toxic cyanobacteria (Microcystis and Dolichospermum). In low-stability lakes, more diverse water quality indicators are correlated with the development of toxic algae than in high-stability lakes. This paper is the first report on the importance of algal community stability in freshwater in the occurrence of toxic cyanobacteria and offers a new perspective on Microcystis monitoring and management.

Accumulation of Microcystin (LR, RR and YR) in Three Freshwater Bivalves in Microcystis aeruginosa Bloom Using Dual Isotope Tracer.

Abstract: Stable isotope tracers were first applied to evaluate the Microcystis cell assimilation efficiency of Sinanodonta bivalves, since the past identification method has been limited to tracking the changes of each chl-a, clearity, and nutrient. The toxicity profile and accumulation of MC-LR, -RR and -YR in different organs (foot and digestive organs) from the three filter-feeders (Sinanodonta woodina, Sinanodonta arcaeformis, and Unio douglasiae) were assessed under the condition of toxigenic cyanobacteria (Microcystis aeruginosa) blooms through an in situ pond experiment using 13C and 15N dual isotope tracers. Chl-a concentration in the manipulated pond was dramatically decreased after the beginning of the second day, ranging from 217.5 to 15.6 µg·L-1. The highest amount of MCs was incorporated into muscle and gland tissues in U. douglasiae during the study period, at nearly 2 or 3 times higher than in S.woodiana and S. arcaeformis. In addition, the incorporated 13C and 15N atom % in the U. douglasiae bivalve showed lower values than in other bivalves. The results demonstrate that U. douglasiae has less capacity to assimilate toxic cyanobacteria derived from diet. However, the incorporated 13C and 15N atom % of S. arcaeformis showed a larger feeding capacity than U. douglasiae and S. wodiana. Our results therefore also indicate that S. arcaeformis can eliminate the toxin more rapidly than U. douglasiae, having a larger detoxification capacity.

Removal of cyanobacteria and microcystin by natural plant-mineral combinations in eutrophic waters.

The removal or mitigation of cyanobacterial bloom and cyanotoxins is a necessity to ensure safe drinking water and recreational water. As a feasible agent to control cyanobacterial bloom, a novel plant-mineral composite (PMC) was developed and optimized through laboratory and field testing over the past 3 years. Based on previous studies, we treated cyanobacterial bloom water (mainly Microcystis and Synechocystis) with 0.05 mg/L PMC at the small eutrophic reservoir; 2 h later, we collected samples and analyzed them in the laboratory. The intra-cellular (c-MC) and dissolved microcystin-LR (d-MC) were measured using an ELISA method. The PMC exhibited a remarkable removal of both c-MC (47.3 %) and d-MC (95.8 %) within 2 days. In addition, notable decreases (on average, 78 % of the control) in the chlorophyll-a, suspended solids, total phosphorus and biochemical oxygen demand values, in zooplankton and in the phytoplankton density (83.9 %) were verified after 48 h. These results indicate that the PMC is more effective in controlling d-MC than c-MC, suggesting a possible method to mitigate such hazardous chemicals as agrochemicals and endocrine disrupters in aquatic ecosystems.

Downstream Transport of Geosmin Based on Harmful Cyanobacterial Outbreak Upstream in a Reservoir Cascade.

Understanding water quality events in a multiple-impoundment series is important but seldom presented comprehensively. Therefore, this study was conducted to systematically understand the explosion event of geosmin (GSM) in the North Han River (Chuncheon, Soyang, Euiam, and Cheongpyeong Reservoirs) and Han River (Paldang Reservoir), which consists of a cascade reservoir series, the largest drinking water source system in South Korea. We investigated the spatiotemporal relationship of harmful cyanobacterial blooms in the upstream reservoir (Euiam) with the water quality incident event caused by the GSM in the downstream reservoir (Paldang) from January to December 2011. The harmful cyanobacterial bloom occurred during August−September under a high water temperature (>20 °C) after a heavy-rainfall-based flood runoff event. The high chlorophyll-a (Chl-a) concentration in the upper Euiam Reservoir was prolonged for two months with a maximum concentration of 1150.5 mg m−3, in which the filamentous Dolichospermum circinale Kütz dominated the algal community at a rate of >99%. These parameters remarkably decreased (17.3 mg Chl-a m−3) in October 2011 when the water temperature decreased (5 °C) and soluble reactive phosphorus was depleted. However, high and unprecedented GSM concentrations, with a maximum value of 1640 ng L−1, were detected in the downstream reservoirs (Cheongpyeong and Paldang); the level was 11 times higher than the value (10 ng L−1) recommended by the World Health Organization. The concentrations of GSM gradually decreased and had an adverse effect on the drinking water quality until the end of December 2011. Our study indicated that the time lag between the summer−fall cyanobacterial outbreak in the upstream reservoir and winter GSM explosion events in the downstream reservoirs could be attributed to the transport and release of GSM through the effluent from hydroelectric power generation in this multiple-reservoir system. Therefore, we suggest that a structural understanding of the reservoir cascade be considered during water quality management of drinking water sources to avoid such incidents in the future.

Shift in nutrient and plankton community in eutrophic lake following introduction of a freshwater bivalve.

The impact of the freshwater bivalve Corbicula leana on plankton community dynamics was examined during a cyanobacterial bloom period. Nutrient and chlorophyll concentrations, primary productivity, and phytoplankton and zooplankton communities in the experimental enclosures were measured at 2-3 day intervals. The introduction of mussels reduced net primary productivity and phytoplankton and chlorophyll. Chlorophyll decreased immediately following addition of 100 mussels and then increased over time. After 600 mussels were added, chlorophyll decreased continuously from 87to 25 microg l(-1), approaching that in the mussel-free enclosure. Simultaneously, water transparency increased and concentrations of suspended solids and total phosphorus decreased. Mussel addition caused short-term increases in nutrient concentrations, especially following high-density treatment: phytoplankton density decreased, while cell density in the mussel-free enclosure increased. Zooplankton densities in the two enclosures were similar; however, carbon biomass in the mussel enclosure increased, associated with an increase in large zooplankton. The trophic relationship between phytoplankton and zooplankton was positive in the mussel-free enclosure and negative in the mussel-treatment enclosure, possibly reflecting effects of mussels on both consumer and resource control in the plankton community. Thus, filter feeding by Corbicula affects nutrient recycling and plankton community structure in a freshwater ecosystem through direct feeding and competition for food resources.

Selective inhibitory potential of silver nanoparticles on the harmful cyanobacterium Microcystis aeruginosa.

Silver nanoparticles (SNPs) at 1 mg/l inhibited the growth of the toxic cyanobacterium, Microcystis aeruginosa, by 87%. Similar results were obtained in field experiments. M. aeruginosa was more sensitive to SNPs than were green algae. SNPs may be a useful selective biocidal agent for the control of M. aeruginosa.

Relationship between cyanobacterial biomass and total microcystin-LR levels in drinking and recreational water.

Cyanobacterial biomass, chlorophyll-a, and microcystin-LR levels were monitored in drinking and recreational water in Seoul, South Korea and three satellite cities from Oct 2006 to Aug 2007. Total microcystin-LR was the sum of particulate and dissolved microcystin. Except during cold periods, toxic cyanobacteria, including Anabaena flos-aquae, were found at all sites. The total microcystin-LR levels were below guideline danger levels (<1.0 µg/L) except one time (1.27 µg/L in October), whereas chl-a (111.7 µg/L) and cell levels (2.6 × 105 cells/mL) were at 'vigilance' and 'alert' levels for drinking water and at 'guidance' level for recreational water, respectively. Discrepancies in these parameters may thus lead to frequent unnecessary alerts, thereby increasing water management costs.

Effects of cyanobacterium Microcystis aeruginosa on the filtration rate and mortality of the freshwater bivalve Corbicula leana.

We compared filtering rates (FR) and mortalities between freshwater filter-feeding bivalve Corbicula leana acclimatized (AM) and non-acclimatized (NAM) to an cyanobacterial bloom (mainly Microcystis aeruginosa) over seven days. Both mussel populations were simultaneously stocked into mesocosms constructed in littoral zones of a eutrophic lake at a density of 740 ind. m(-2) for 16 days. NAMs decreased the concentration of chlorophyll-a 50% less than AMs. For the first seven days, the FRs (0.46-0.61) and mortality rate (slope = -30.2, r = -0.95) of NAMs were higher than those of AMs, possibly due to a sudden increase in unselective filtering. From the eighth day NAM mortality decreased rapidly and then stabilized, becoming similar to that of AMs through the end of the experiment. Stocking both AMs and NAMs increased the NH4-N concentration in the water, and the mortality rates of both mussel populations were correlated with NH4-N. In contrast, other nutrients and microcystin concentrations were not significantly associated with mussel mortality. These results indicate that although a sudden introduction of non-acclimatized C. leana may partially control phytoplankton biomass fora short period, previous short-term acclimatization is needed to minimize mussel mortality.

Eutrophication and the Ecological Health Risk.

This Special Issue focuses on eutrophication and related ecological health risks-one of the biggest challenges to sustainable water management. It is increasingly recognized that eutrophication has multidimensional consequences for water quality, both ecosystem and human health, as well as economic activities. These consequences depend on site-specific conditions, specifically, the ecological stability of the system, land use types, climate change, and the presence of other contaminants, including infectious disease agents. This Special Issue contains ten research papers that focus on, among other factors, phosphorus, cyanobacteria, off-flavor substances, macroinvertebrates, chemical stress, and land-use effects, thereby increasing our understanding of the multidimensional effects of eutrophication.

Heterocyst Development and Diazotrophic Growth of Anabaena variabilis under Different Nitrogen Availability.

Nitrogen is globally limiting primary production in the ocean, but some species of cyanobacteria can carry out nitrogen (N) fixation using specialized cells known as heterocysts. However, the effect of N sources and their availability on heterocyst development is not yet fully understood. This study aimed to evaluate the effect of various inorganic N sources on the heterocyst development and cellular growth in an N-fixing cyanobacterium, Anabaena variabilis. Growth rate, heterocyst development, and cellular N content of the cyanobacteria were examined under varying nitrate and ammonium concentrations. A. variabilis exhibited high growth rate both in the presence and absence of N sources regardless of their concentration. Ammonium was the primary source of N in A. variabilis. Even the highest concentrations of both nitrate (1.5 g L-1 as NaNO3) and ammonium (0.006 g L-1 as Fe-NH4-citrate) did not exhibit an inhibitory effect on heterocyst development. Heterocyst production positively correlated with the cell N quota and negatively correlated with vegetative cell growth, indicating that both of the processes were interdependent. Taken together, N deprivation triggers heterocyst production for N fixation. This study outlines the difference in heterocyst development and growth in A. variabilis under different N sources.

Molecular Probes to Evaluate the Synthesis and Production Potential of an Odorous Compound (2-methylisoborneol) in Cyanobacteria.

The volatile metabolite, 2-Methylisoborneol (2-MIB) produced by cyanobacterial species, causes odor and taste problems in freshwater systems. However, simple identification of cyanobacteria that produce such off-flavors may be insufficient to establish the causal agent of off-flavor-related problems as the production-related genes are often strain-specific. Here, we designed a set of primers for detecting and quantifying 2-MIB-synthesizing cyanobacteria based on mibC gene sequences (encoding 2-MIB synthesis-catalyzing monoterpene cyclase) from various Oscillatoriales and Synechococcales cyanobacterial strains deposited in GenBank. Cyanobacterial cells and environmental DNA and RNA were collected from both the water column and sediment of a eutrophic stream (the Gong-ji Stream, Chuncheon, South Korea), which has a high 2-MIB concentration. Primer sets mibC196 and mibC300 showed universality to mibC in the Synechococcales and Oscillatoriales strains; the mibC132 primer showed high specificity for Pseudanabaena and Planktothricoides mibC. Our mibC primers showed excellent amplification efficiency (100-102%) and high correlation among related variables (2-MIB concentration with water RNA r = 689, p < 0.01; sediment DNA r = 0.794, p < 0.01; and water DNA r = 0.644, p < 0.05; cyanobacteria cell density with water RNA and DNA r = 0.995, p < 0.01). These primers offer an efficient tool for identifying cyanobacterial strains possessing mibC genes (and thus 2-MIB-producing potential) and for evaluating mibC gene expression as an early warning of massive cyanobacterial occurrence.

Response of Scenedesmus quadricauda (Chlorophyceae) to Salt Stress Considering Nutrient Enrichment and Intracellular Proline Accumulation.

Aquatic organisms are exposed to a wide range of salinity, which could critically affect their survival and growth. However, their survival and growth response to salinity stress remain unclear. This study evaluates the growth response and intracellular proline accumulation of green algae, Scenedesmus quadricauda, isolated from brackish water, against dissolved salts stress with N and P enrichment. We tested a hypothesis that nutrient enrichment can relieve the dissolved salts stress of algae by accumulating intracellular proline, thereby improving survival and growth. Four levels of salinity (0, 3, 6, 12 psu) were experimentally manipulated with four levels of nutrient stoichiometry (N:P ratio = 2, 5, 10, 20) at constant N (1 mgN/L) or P levels (0.05 and 0.5 mgP/L). In each set of experiments, growth rate and intracellular proline content were measured in triplicate. The highest level of salinity inhibited the growth rate of S. quadricauda, regardless of the nutrient levels. However, with nutrient enrichment, the alga showed tolerance to dissolved salts, reflecting intracellular proline synthesis. Proline accumulation was most prominent at the highest salinity level, and its maximum value appeared at the highest N:P ratio (i.e., highest N level) in all salinity treatments, regardless of P levels. Therefore, the effects of P and N on algal response to salt stress differ.

An Estimated Structural Equation Model to Assess the Effects of Land Use on Water Quality and Benthic Macroinvertebrates in Streams of the Nam-Han River System, South Korea.

The extent of anthropogenic land use in watersheds determines the amount of pollutants discharged to streams. This indirectly and directly affects stream water quality and biological health. Most studies have therefore focused on ways to reduce non-point pollution sources to streams from the surrounding land use in watersheds. However, the mechanistic pathways between land use and the deterioration of stream water quality and biological assemblages remain unclear. This study estimated a structural equation model (SEM) representing the impact of agricultural and urban land use on water quality and the benthic macroinvertebrate index (BMI) using IBM AMOS in the Nam-Han river systems, South Korea. The estimated SEM showed that the percent of urban and agricultural land in the watersheds significantly affected both the water quality and the BMI of the streams. Specifically, a higher percent of urban land use had directly increased the biochemical oxygen demand (BOD) and total phosphorus (TP), and deteriorated the BMI of streams. Similarly, higher proportions of agricultural land use had also directly increased the BOD, total nitrogen (TN), and total phosphorus (TP) concentrations, and lowered the BMI of streams. In addition, it was observed that the percent of urban and agricultural land use had indirectly deteriorated the BMI through increased BOD. However, we were not able to observe any significant indirect effect of the percent of urban and agricultural land use through increased nutrients including TN and TP. These results indicate that increased urban and agricultural land use in the watersheds had directly and indirectly affected the physicochemical characteristics and benthic macroinvertebrate communities in streams. Our findings emphasize the need to develop more elaborate environmental management and restoration strategies to improve the water quality and biological status of streams.

Selective bactericidal potential of rice (Oryza sativa L. var. japonica) hull extract on Microcystis strains in comparison with green algae and zooplankton.

We examined the selective inhibitory potential of rice hull extract on the toxic cyanobacterium Microcystis aeruginosa, in comparison with inhibitory effects on two green algae (Ankistrodesmus convolutus and Scenedesmus quadricauda) and a zooplankton (Daphnia magna) species. The inhibitory effect of rice hull extract, measured by algal growth or zooplankton survival using four different concentrations of extract (1, 10, 100 and 1000 microg L(-1)), was highest on Microcystis strains (average: 98%, range: 95%-99%), followed by D. magna (average: 22%, range: 10%-47%), A. convolutus (average: 20%, range: 16%-24%), and S. quadricauda (average: 8%, range: 0%-15%). Rice hull extract had only a small effect on the growth of the green algae and Daphnia, particularly in the range 1-100 microg L(-1), and the inhibitory effect was somewhat diminished even at the 1,000 microg L(-1) level, at the end of the experimental period, especially for Daphnia. Our study indicates that rice hull extract has a strong specific algicide potential when used to combat M. aeruginosa.

Effects of Microbial Activity and Environmental Parameters on the Degradation of Extracellular Environmental DNA from a Eutrophic Lake.

Extracellular DNA (exDNA) pool in aquatic environments is a valuable source for biomonitoring and bioassessment. However, degradation under particular environmental conditions can hamper exDNA detectability over time. In this study, we analyzed how different biotic and abiotic factors affect the degradation rate of extracellular environmental DNA using 16S rDNA sequences extracted from the sediment of a eutrophic lake and Anabaena variabilis cultured in the laboratory. We exposed the extracted exDNA to different levels of temperature, light, pH, and bacterial activity, and quantitatively analyzed the concentration of exDNA during 4 days. The solution containing bacteria for microbial activity treatment was obtained from the lake sediment using four consecutive steps of filtration; two mesh filters (100 µm and 60 µm mesh) and two glass fiber filters (2.7 µm and 1.2 µm pore-sized). We found that temperature individually and in combination with bacterial abundance had significant positive effects on the degradation of exDNA. The highest degradation rate was observed in samples exposed to high microbial activity, where exDNA was completely degraded within 1 day at a rate of 3.27 day-1. Light intensity and pH had no significant effects on degradation rate of exDNA. Our results indicate that degradation of exDNA in freshwater ecosystems is driven by the combination of both biotic and abiotic factors and it may occur very fast under particular conditions.

Harmful Cyanobacterial Material Production in the North Han River (South Korea): Genetic Potential and Temperature-Dependent Properties.

Cyanobacteria synthesize various harmful materials, including off-flavor substances and toxins, that are regarded as potential socio-economic and environmental hazards in freshwater systems, however, their production is still not well understood. In this study, we investigated the potential and properties of harmful materials produced by cyanobacteria, depending on temperature, and undertook a phylogenetic analysis of cyanobacteria present in the North Han River (South Korea). Production potentials were evaluated using gene-specific probes, and the harmful material production properties of strains showing positive potentials were further characterized at different temperatures in the range 15 to 30 °C. We identified six cyanobacterial strains based on 16S rDNA analysis: two morphological types (coiled and straight type) of Dolichospermum circinale, Aphanizomenon flos-aquae, Oscillatoria limosa, Planktothricoides raciborskii, Pseudanabaena mucicola, and Microcystis aeruginosa. We confirmed that cyanobacterial strains showing harmful material production potential produced the corresponding harmful material, and their production properties varied with temperature. Total harmful material production was maximal at 20~25 °C, a temperature range optimal for cell growth. However, harmful material productivity was highest at 15 °C. These results indicate that the expression of genes related to synthesis of harmful materials can vary depending on environmental conditions, resulting in variable harmful material production, even within the same cyanobacterial strains.

Distribution Patterns of Odonate Assemblages in Relation to Environmental Variables in Streams of South Korea.

Odonata species are sensitive to environmental changes, particularly those caused by humans, and provide valuable ecosystem services as intermediate predators in food webs. We aimed: (i) to investigate the distribution patterns of Odonata in streams on a nationwide scale across South Korea; (ii) to evaluate the relationships between the distribution patterns of odonates and their environmental conditions; and (iii) to identify indicator species and the most significant environmental factors affecting their distributions. Samples were collected from 965 sampling sites in streams across South Korea. We also measured 34 environmental variables grouped into six categories: geography, meteorology, land use, substrate composition, hydrology, and physicochemistry. A total of 83 taxa belonging to 10 families of Odonata were recorded in the dataset. Among them, eight species displayed high abundances and incidences. Self-organizing map (SOM) classified sampling sites into seven clusters (A⁻G) which could be divided into two distinct groups (A⁻C and D⁻G) according to the similarities of their odonate assemblages. Clusters A⁻C were characterized by members of the suborder Anisoptera, whereas clusters D⁻G were characterized by the suborder Zygoptera. Non-metric multidimensional scaling (NMDS) identified forest (%), altitude, and cobble (%) in substrata as the most influential environmental factors determining odonate assemblage compositions. Our results emphasize the importance of habitat heterogeneity by demonstrating its effect on odonate assemblages.

Comparative assessment of the adverse outcome of wastewater effluents by integrating oxidative stress and histopathological alterations in endemic fish.

This study evaluated the adverse effect of wastewater effluents on three fish species, Carassius auratus, Zacco platypus, and Zacco koreanus, collected in the Eungcheon, Mihocheon, and Busocheon streams, respectively. Fish gills, liver, and kidneys from the mixing zone (MZ) and sites upstream (US) and downstream (DS) of the MZ were analyzed for oxidative stress responses and histology. Catalase and glutathione S-transferase activity was significantly higher at MZ and DS than from US (p<0.05), indicating induction of antioxidant defense mechanisms. Additionally, degree of tissue changes (DTC) indicated highest histopathological alteration in MZ, followed by DS and US. Integrated biomarker response (IBR) for oxidative stress and histopathological alterations showed higher values consistently for Z. koreanus than other two species. Water temperature, EC, and TN levels seemed to be responsible for the observed biomarker responses. These findings indicate that thermal hot spring effluent discharged into Busocheon steam induced the most significant impact on the cool water species (Z. koreanus). Overall, this study suggests that the IBR index is a very useful tool for monitoring in situ adverse effects of wastewater effluents on fish, particularly for histopathological alterations representing prolonged impact.