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Abstract Background Red pepper paste is a common ingredient used in food in Korea. The discrimination of the geographical origin of agricultural products is important to protect the agricultural industry and customers from the misinformation regarding the product origin. Several studies have attempted to identify the geographical origin of red pepper based on its characteristic features using diverse methods, such as inorganic elemental analysis. However, similar studies on red pepper pastes have not been conducted thus far. Results In, this study, we established methods based on inductively coupled plasma optical emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) for determining inorganic elements in red pepper pastes. The limit of detection (LOD) of ICP-AES was in the range of 0.006–0.531 mg∙kg−1 and the limit of quantification (LOQ) was 0.017–1.593 mg∙kg−1. In addition, LOD and LOQ ranges for ICP-MS were 0.001–1.553, and 0.002–5.176 μg∙kg−1, respectively. The concentrations of Ca, K, Mg, Na, P, S, Cr, Mn, Co, Ni, Cu, Ga, As, Sr, Zr, Mo, Pd, Cd, Sn, Sb, Ce, Pt, Pb, and U were high in the Korean red pepper paste. All the employed discrimination models could clearly distinguish between Korean and Chinese red pepper pastes. In particular, among the four different models, CDA showed the most accurate ability to discriminate the geological origin of Korean and Chinese red pepper paste compared to that achieved using the other models with 100% accuracy. Conclusions Based on, the findings of this study, the use of ICP-AES and ICP-MS analyses for discriminating the inorganic elements in food products in combination with the aforementioned statistical analysis models could help the mitigation of issues associated with the misinformation of the geographical origin of agricultural products, aiding customer protection. Graphical Abstract

Pyrochar (Biochar) produced from the thermochemical conversion of biomass has been widely used as a soil amendment to improve agricultural soil quality. Since polycyclic aromatic hydrocarbons (PAHs) can be produced in such processes, the occurrence of PAHs in pyrochars has been extensively studied, and standards such as the European Biochar Certificate (EBC) and International Biochar Initiative (IBI) contain limit values for biochars applied to soils. However, studies on PAH levels in hydrochars from hydrothermal processes, which can be an alternative to wet biomass are scarce. This study focuses on comparing the occurrence of 16 PAHs regulated by the US EPA in 22 char samples (including pyrochars from pyrolysis, hydrochars from hydrothermal carbonization, and, for the first time, hydrothermal humification) using an ultrasonic extraction method. Results showed that the sum of the 16 EPA PAHs in all samples was well below the requirements of the two standards, except for pyrochar produced at the farm scale. They ranged from 131 to 9358 µg·kg−1 in the seven pyrochars and from not detected to 333 µg·kg−1 for the fourteen hydrochars. Our findings indicate that hydrochar produced via hydrothermal methods exhibits much lower concentrations and is a safe option for soil amendment and environmental applications.

Abstract Background Ethyl formate (EF) is naturally occurring volatile compound used as quarantine fumigant for pest control. Recently, conversion of uses of EF was tried from quarantine to agricultural field due to its promising efficacy. However, there is a lack of studies on the residue pattern on crops and soil and the phytotoxic mechanism of EF in greenhouse environment. This study aimed to evaluate the efficacy, residue analysis, and phytotoxicity of EF fumigation in controlling Myzus persicae and Thrips palmi, on cucurbit crops and establish an optimized fumigation strategy for use in greenhouses. Results The results showed that EF was more effective against M. persicae than against T. palmi. Residue analysis indicated that EF rapidly decomposed and was not retained after 30 min in leaves and 2 h in soil after fumigation, suggesting the potential for residue-free pest control. Phytotoxicity test revealed that watermelon was the most sensitive crop to EF, and H2O2 accumulation was observed above a concentration of 7.5 g/m3. A strategy to reduce phytotoxicity with sodium bicarbonate during fumigation showed promising results in reducing phytotoxic effects on the crops. The optimized EF fumigation with 6 g/m3 was applied in a greenhouse, resulting in 100% and 40% mortality of M. persicae and T. palmi, respectively, with no notable phytotoxicity and EF residue in the treated crops and soil. Conclusion This study demonstrates that optimized EF fumigation can be an environmentally sustainable method for controlling pests in greenhouses, paving the way for improved pest management practices and sustainable agriculture. Further research is needed to validate these findings and explore the potential of EF fumigation for other crops and pests. Graphical Abstract

Piperlongumine (PL) and piperine (PP) are alkaloids presented in long pepper (Piper longum), and they exhibit various biological activities, especially anti-cancer properties. With these regards, they are considered as future medicines with high potential. Even they are exposed to humans such a long time, their potential toxicities in the environment have not been studied. Therefore, their ecological toxicities were assessed using zebrafish embryos. PP showed low mortality and no abnormal phenotype up to 10 µM. However, PL exhibited strong acute toxicity at the concentration of 5–10 µM ranges, and abnormal development were frequently found in the range of 1–2.5 µM with pericardial and yolk sac edemas. In transgenic zebrafish embryos, PL induced an increase in the number of intersegmental vessels and delayed the early-stage development. PL treatment affected heart formation and heart rate. The presence of PL induced the expression of cytokines, inflammatory markers, and inflammasome in the embryos. The PL treatment changed the mRNA levels of the ER stress and apoptosis-related genes. In addition, ROS production was observed during early-stage development of PL-treated zebrafish embryos. These results indicate that developing PL as a medicine would require extremely meticulous strategies to prevent potential toxicity.

Pymetrozine (PYM) is worldwide used to control sucking insect pests in rice-cultivated fields and it is degraded into various metabolites including 3-pyridinecarboxaldehyde (3-PCA). These two pyridine compounds were used to determine their impacts on aquatic environments, particularly on the aquatic animal model zebrafish (Danio rerio). PYM did not show acute toxicities in terms of lethality, hatching rate, and phenotypic changes in zebrafish embryos in the tested ranges up to a concentration of 20 mg/L. 3-PCA exhibited acute toxicity with LC50 and EC50 values of 10.7 and 2.07 mg/L, respectively. 3-PCA treatment caused phenotypic changes including pericardial edema, yolk sac edema, hyperemia, and curved spine, at a concentration of 10 mg/L after 48 h of exposure. Abnormal cardiac development was observed in 3-PCA-treated zebrafish embryos at a concentration of 5 mg/L with reduced heart function. In a molecular analysis, cacna1c, encoding a voltage-dependent calcium channel, was significantly down-regulated in the 3-PCA-treated embryos, indicating synaptic and behavioral defects. Hyperemia and incomplete intersegmental vessels were observed in 3-PCA-treated embryos. Based on these results, it is necessary to generate scientific information on the acute and chronic toxicity of PYM and its metabolites with regular monitoring of their residues in aquatic environments.

Chlorpyrifos-methyl (CPM) is one of the thiophosphate insecticides, and it is mainly metabolized to 3,5,6-trichloro-2-pyridinol (TCP) in the environment. As CPM is a strongly toxic and TCP is persistent in the environment, CPM and TCP need to be evaluate their toxicities using animal model organisms. With this regard, CPM and TCP were treated on zebrafish (Danio rerio) embryos and LC50 values were determined as over 2000 μg/L and 612.5 μg/L, respectively. For the hatchability, CPM did not exhibit any interference, while TCP showed weak inhibition. In the CPM-treated embryos, pericardial edema and bleeding were observed at 48 hpf, but recovered afterwards. The pericardial edema and yolk sac edema were observed in TCP-treated zebrafish embryos at the concentration of 500 μg/L after 72 hpf. TCP induced abnormal heart development and the heartbeat was dramatically decreased in Tg(cmlc2:EGFP) embryos at the level of 500 μg/L. The expression level of heart development-related genes such as gata, myl7, and cacna1c was significantly decreased in the TCP 500 μg/L-treated embryos at the 96 hpf. Taken together, TCP appears to be more toxic than the parent compound towards the zebrafish embryos. It is highly requested that TCP needs to be monitored with a strong public concern because it affects presumably heart development in early-stage aquatic vertebrates.

This dataset contains raw and analyzed microbial data for the samples of spontaneously fermented Ethiopian honey wine, Tej, collected from three locations of Ethiopia. It was generated using culture independent amplicon sequencing technique. To gain a better understanding of microbial community variance and similarity across Tej samples from the same and different locations, the raw sequenced data obtained from the Illumina Miseq sequencer was subjected to a bioinformatics analysis. Lower diversity and richness of both bacterial and fungal communities were observed for all of the Tej samples. Besides, samples collected from Debre Markos area showed a significant discriminating tax for both bacterial and fungal communities. In nutshell, this amplicon sequencing dataset provides a useful collection of data for modernizing this spontaneous fermentation into a directed inoculated fermentation. Detail discussion on microbiome of Tej samples is given in [1].

Regulation of melanin production via the MC1R signaling pathway is a protective mechanism of the skin of living organisms against exposure to ultraviolet rays. The discovery of human skin-whitening agents has been one of the most intense pursuits of the cosmetic industry. The MC1R signaling pathway is activated by its agonist, alpha-melanocyte stimulating hormone (α-MSH), and mainly regulates melanogenesis. Here, we evaluated the antimelanogenic activities of curcumin (CUR) and its two derivatives, dimethoxycurcumin (DMC) and bisdemethoxycurcumin (BDMC), in B16F10 mouse melanoma cells and zebrafish embryos. CUR and BDMC reduced the α-MSH-induced melanin production in B16F10 cells and also downregulated the expression of the melanin-production-related genes Tyr, Mitf, Trp-1, and Trp-2. Moreover, the biological activity of these two compounds against melanogenesis was confirmed in in vivo experiments using zebrafish embryos. However, the highest concentration of CUR (5 µM) resulted in slight malformations in zebrafish embryos, as indicated by acute toxicity tests. In contrast, DMC did not show any biological activity in vitro or in vivo. Conclusively, BDMC is a strong candidate as a skin-whitening agent.

Pyrethroid and organochlorine insecticides are enormously used to control agricultural and indoor insect pests. The metabolites of pyrethroid and endosulfan were used to evaluate environmental toxicities using a representative animal model, zebrafish (Danio rerio) embryos in this study. The LC50 values in 3-phenoxy benzoic acid (3-PBA) and endosulfan sulfate (ES) were 1461 μg/L and 1459 μg/L, respectively. At the concentration of 2000 μg/L, spine curvature was observed in the ES-treated embryos. ES showed seizure-like events with an EC50 value of 354 μg/L. At the concentration of 1000 μg/L, the pericardial edema was observed in 3-PBA-treated embryos. The inhibition of heart development and the reduction of beating rates were observed in Tg(cmlc2:EGFP) embryos after the exposure to 3-PBA. Down-regulation of the vmhc gene coding ventricular myosin during heart development was significantly found in 3-PBA-treated embryos at 48 hpf, but recovered afterward. It indicates that ventricular malformation occurred at the initial stage of 3-PBA exposure. Considered together, both 3-PBA and ES need public concerns with periodic monitoring of these metabolites in households and agricultural areas to prevent humans and environmental organisms from their unexpected attacks.

Toxicological studies of O-ethyl-O-(4-nitrophenyl) phenylphosphonothioate (EPN) to aquatic vertebrates have been reported, but no reports on toxic mechanism was reported. As zebrafish (Danio rerio) embryos were exposed to EPN, no changes in their survival and hatching rates were observed until 96 h post fertilization (hpf), even at the highest treated concentration of 500 μg/L. In both 250 μg/L and 500 μg/L, edemas were observed in the heart and yolk sac, and a blood pool was also found. Acridine orange staining confirmed apoptotic phynotype, which was the strongest in embryos at 48 hpf. No noticeable difference in the formation and the shape of blood vessels of Tg(fli1a:EGFP) was observed. However, the total body length and number of somite were decreased. Heart formation in Tg(cmlc2:EGFP) were not properly proceeded, and the ventricle did not beat normally at 500 μg/L level. Cardiac development-related genes, myl7 and nppa, were significantly down- and up-regulated in a concentration-dependent manner. The slowed heartbeat was confirmed using Tg(gata1:EGFP), showing stagnant blood flow and seizure-like events were observed. Altogether, EPN can be the cause for the abnormal heart development accompanied by blood stagnation in embryos, interfering normal development with their inner circulatory system.

Abstract Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants that are released by incomplete combustion of carbon-containing materials. The top soils of rice paddies were collected from Gyeonggi-do (18 sites), Ulsan (20 sites), and Pohang (19 sites) in Korea to assess the spatial distribution and potential sources of PAHs. The total concentrations of 15 PAHs in the soils were 19.53–672.93, 125.01–3106.27, and 51.94–8106.21 mg/kg in Gyeonggi province, Ulsan, and Pohang, respectively. The concentration of 7 key carcinogenic PAHs were followed the order: Pohang (38.54–4826.63 ng/g) > Ulsan (28.54–1561.39 ng/g) > Gyeonggi province (19.53–206.51 ng/g). Three-ring PAHs were predominant in the soils from Gyeonggi-do while 3–5 ring compounds were abundant in the agricultural soils from the two industrial regions (Ulsan and Pohang). The PAH isomeric diagnostic ratios indicated that PAH contamination in the two cities mainly originated from pyrogenic sources. The principal component analysis indicated that pyrogenic coal burning and residential biomass combustion were major contributors to the soil contamination in the two cities. The transportation of PAHs through the air from industrial complexes and high volume of traffic may influence the PAHs distribution in the soils of the two cities in Korea.

Methyl bromide (MB) has been used in a wide range of applications, but since it was determined to be an ozone-depleting compound, it has only been used for pre-shipment and quarantine purposes in trade. Phosphine (PH3) is currently the ideal fumigant as an MB alternative worldwide. However, the development of PH3 resistance in the target insect pest and longer PH3 fumigation treatment times raise questions about the continued use of PH3. This study attempted to shorten treatment time via combination treatment with ethyl formate (EF). Planococcus citri was used as the main quarantine pest in Korea, and the acute toxicity of EF, PH3, and EF + PH3 was determined at every developmental stage. EF treatment at 4 h showed LCT99 values of 45.85~65.43 mg∙h/L, and PH3 treatment at 20 h showed that of 0.13~0.83 mg∙h/L depending on the developmental stage. The efficacy of PH3 decreased after reducing the treatment time, but synergistic effects were observed at all stages of development of P. citri when both fumigants were used simultaneously for 4 h. After combined treatment, dihydrolipoyl dehydrogenase expression and the production of two phospholipids, PI(O-16:0) and PC(18:2), were significantly reduced in treated P. citri adults compared with the control. Therefore, combined treatments might be key to reducing the treatment time and resistance of PH3 in the field.

Pesticides have been used to control pests in agricultural fields and storage systems before circulating agricultural products to markets. A tandem mass spectrometry, equipped with gas chromatographic separation (GC–MS/MS) or ultra-performance liquid chromatographic separation (LC–MS/MS), was used to monitor residual pesticides in Korean rice paddy soils. Selective multiple reaction monitoring was employed during the analyses to achieve multiresidue pesticide analysis using GC–MS/MS and LC–MS/MS of 342 pesticides. In this study, QuEChERS extraction was employed with a dSPE clean-up to establish an effective pretreatment process. The limit of detection (LOD) and limit of quantification (LOQ) were set up for all pesticides, and method validation was performed for linearity and recovery at levels of 10 and 50 mg kg−1 in the untreated soil sample. All pesticides satisfied the acceptable recovery range of 70–120%, within less than 20% RSD values, except for ametoctradin and gibberellic acid. In the paddy soil analyses, tricyclazole was the most frequently detectable pesticide, followed by oxadiazon, endosulfan, and chlorantraniliprole. Continuous monitoring of residual pesticides in paddy soils should be conducted due to the translocation of some systemic pesticides from soils to crop plants, and the impact of residual pesticides on the environment.

Melanogenesis represents a series of processes that produce melanin, a protective skin pigment (against ultraviolet rays), and determines human skin color. Chemicals reducing melanin production have always been in demand in the cosmetic market because of skincare interests, such as whitening. The main mechanism for inhibiting melanin production is the inhibition of tyrosinase (TYR), a key enzyme for melanogenesis. Here, we evaluated gedunin (Ged), a representative limonoid, for its anti-melanogenesis action. Melanin production in vitro was stimulated by alpha-melanocyte stimulating hormone (α-MSH) in B16F10 mouse melanoma cells. Ged reduced α-MSH-stimulated melanin production, inhibiting TYR activity and protein amount. We confirmed this result in vivo in a zebrafish model for melanogenesis. There was no sign of toxicity and malformation of zebrafish embryos during development in all treated concentrations. Ged reduced the number of produced zebrafish embryo pigment dots and melanin contents of embryos. The highly active concentration of Ged (100 µM) was much lower than the positive control, kojic acid (8 mM). Hence, Ged could be a fascinating candidate for anti-melanogenesis reagents.

Endosulfan has been listed as a persistent organic pollutant, and is frequently found in agricultural environments during monitoring processes owing to its heavy use and persistent characteristics. This study was conducted to understand the effects of endosulfan on the development of zebrafish (Danio rerio) embryos by exposing them to a specific range of endosulfan concentrations. Exposing zebrafish embryos to endosulfan for 96 h yielded no acute toxicity until the concentration reached 1500 μg L−1, whereas malformed zebrafish larvae developed severely curved spines and shortened tails. About 50% of zebrafish larvae were malformed when exposed to 600 μg L−1 of endosulfan. Comparative gene expression using real-time quantitative polymerase chain reaction was assessed using endosulfan-exposed zebrafish embryos. CYP1A and CYP3A were significantly enhanced in response to endosulfan treatment. Two genes, acacb and fasn, encoding acetyl-CoA carboxylase b and fatty acid synthase proteins, respectively, were also up-regulated after treating zebrafish embryos with endosulfan. These genes are also involved in fatty acid biosynthesis. The genes encoding vitellogenin and Hsp70 increased in a concentration-dependent manner in embryos. Finally, biochemical studies showed that acetylcholinesterase activity was reduced, whereas glutathione S-transferase and carboxylesterase activities were enhanced in zebrafish embryos after endosulfan treatment. These biochemical and molecular biological differences might be used for tools to determine contamination of endosulfan in the aquatic environment.

Pesticidal activities of 4-[5-(2-cyclopropylaminopyrimidin-4-yl)-4-(4-chloro-2-fluoro-phenyl)thiazol-2-yl]-1-methylpiperidine, designated as Comp I, have been determined against a mosquito larva, Culex pipiens pallens, and a phytopathogenic fungus, Phytophthora capsici. Comp I was used as the leading compound in this study. The compounds were synthesized by reacting them with two functional groups, 3-thiophenyl and 2-thiophenyl groups, instead of 4-chloro-2-fluorophenyl group in Comp I. Other functional groups such as 2-aminothiazole, 2-(1-methylpiperazin-4-yl)thiazole, and 2-(piperazin-4-yl)thiazole were also introduced instead of 2-methylpiperidin-4-yl-thiazole of Comp I. Compounds designated as XIII-6~XV-7 were newly synthesized and their structures were confirmed by 1H- and 13C-NMR spectroscopy. Mosquito larvicidal activities of all the synthesized compounds against C. pipiens pallens were examined and Comp I among them showed the strongest larvicidal activity as 0.513 mM of LC50 value. The fungicidal activities of all the synthesized compounds against P. capsici were examined using the whole plant method. Among the XIII-6~XV-7 chemicals, 5-(2-cyclopropylaminopyrimidin-4-yl)-4-(thiophen-2-yl)thiazol-2-amine (VIII-6) showed the most potent antifungal activity in vivo. While the EC50 value of the commercial fungicide dimethomorph was 4.26 μM, EC50 of VIII-6 was 0.94 μM. Therefore, thiazole derivatives can be considered as viable candidates for the control of mosquito larvae and plant diseases.