As an important part of extracellular secondary metabolites, extracellular polymeric substances (EPS) can play a significant role in protecting cells from the threat of exogenous substances, including nanoparticles (NPs). However, the regulation mechanisms of EPS secretion under NPs exposure remain largely unknown. This study investigated the signaling pathways and molecular responses related to EPS secretion of algae (Chlorella pyrenoidosa) upon the exposures to anatase and rutile TiO₂ NPs (nTiO₂-A and nTiO₂-R, respectively) at two similar toxic (20% and 50% of algal growth inhibition) concentrations. The results showed that EPS responded to nTiO₂ stress via excess secretion and compositional variation, and nTiO₂-A induced more EPS secretion than nTiO₂-R at similar toxicity concentrations. The up-regulation of the Ca²⁺ signaling pathway might play a greater role in promoting EPS secretion under nTiO₂-R exposure compared with nTiO₂-A exposure, while the significantly increased intracellular ROS could mainly account for the increased EPS secretion under nTiO₂-A exposure. The up-regulated genes related to biological synthesis and protein metabolism and the enhanced biosynthetic metabolism might be the direct causes of the increased EPS secretion. The increased ROS could have a greater effect on the amino acid metabolism and related genes upon the exposure to nTiO₂-A than nTiO₂-R to induce more EPS secretion. More serious membrane damage caused by nTiO₂-R than nTiO₂-A would affect the intracellular inositol phospholipid metabolism more severely, while the inositol phospholipid pathway and Ca²⁺ signaling pathway might agree and communicate with each other inherently to regulate EPS secretion upon nTiO₂-R exposure. The findings address the regulation mechanisms of algal EPS secretion under nTiO₂ exposure and provide new insights into algal bio-responses to nTiO₂ exposure.

Microcystis blooms and their secondary metabolites microcystins (MCs) occurred all over the world, which have damaged aquatic ecosystems and threatened public health. Techniques to reduce the Microcystis blooms and MCs are urgently needed. This study aimed to investigate the algicidal and inhibitory mechanisms of a red pigment prodigiosin (PG) against the growth and MC-producing abilities of Microcystis aeruginosa (M. aeruginosa). The numbers of Microcystis cells were counted under microscope. The expression of microcystin synthase B gene (mcyB) and concentrations of MCs were determined by quantitative real-time polymerase chain reaction (qRT-PCR) and enzyme linked immunosorbent assay (ELISA) methods, respectively. The inhibitory effects of PG against M. aeruginosa strain FACHB 905 with 50% algicidal concentration (LC50) at 120 h was 0.12 μg/mL. When M. aeruginosa cells exposed to 0.08 μg/mL, 0.16 μg/mL, 0.32 μg/mL PG, the expression of mcyB of M. aeruginosa was down-regulated 4.36, 8.16 and 18.51 times lower than that of the control at 120 h. The concentrations of total MC (TMC) also were 1.66, 1.72 and 5.75 times lower than that of the control at 120 h. PG had high algicidal effects against M. aeruginosa, with the activities of superoxide dismutase (SOD) initially increased and then decreased after 72 h, the contents of malondialdehyde (MDA) increase, the expression of mcyB gene down-regulation, and MCs synthesis inhibition. This study was first to report the PG can simultaneously lyse Microcystis cells, down-regulate of mcyB expression and inhibit MCs production effectively probably due to oxidative stress, which indicated PG poses a great potential for regulating Microcystis blooms and MCs pollution in the environment.

Glyphosate, one of the most popular herbicides, has become a prominent aquatic contaminant because of its huge usage. The eco-safety of glyphosate is still in controversy, and it is inconclusive how glyphosate influences aquatic microbial communities. In the present study, the effects of glyphosate on the structure and function of microbial communities in a freshwater microcosm were investigated. 16S/18S rRNA gene sequencing results showed that glyphosate treatment (2.5 mg L⁻¹, 15 days) did not significantly alter the physical and chemical condition of the microcosm or the composition of the main species in the community, but metatranscriptomic analyses indicated that the transcriptions of some cyanobacteria were significantly influenced by glyphosate. The microbial community enhanced the gene expression in pathways related to translation, secondary metabolites biosynthesis, transport and catabolism to potentially withstand glyphosate contamination. In the low phosphorus (P) environment, a common cyanobacterium, Synechococcus, plays a special role by utilizing glyphosate as P source and thus reducing its toxicity to other microbes, such as Pseudanabaena. In general, addition of glyphosate in our artificial microcosms did not strongly affect the aquatic microbial community composition but did alter the community’s transcription levels, which might be potentially explained by that some microbes could alleviate glyphosate’s toxicity by utilizing glyphosate as a P source.

Chinese dark tea is widely enjoyed for its multiple health-promoting effects and pleasant taste. However, its production involves fermentation by microbiota in raw tea, some of which are filamentous fungi and thus potential mycotoxin producers. Accordingly, whether mycotoxins pose health risk on dark tea consumption has become a public concern. In this study, a cleaning method of multi-functional column (MFC) and immunoaffinity column (IAC) in tandem combined to HPLC detection was developed and validated for determining ten mycotoxins of six groups (i.e., aflatoxins of B₁, B₂, G₁ and G₂, ochratoxin A, zearalenone, deoxynivalenol, fumonisins of B₁, B₂, and T-2) in dark teas. The interferences from secondary metabolites were effectively reduced, and the sensitivities and recoveries of the method were qualified for tea matrices. Six groups mycotoxins were determined in 108 samples representing the major Chinese dark teas by using the new method. Subsequently, the dietary exposure and health risks were evaluated for different age and gender groups in Kunming and Pu’er in China and Ulan Bator in Mongolia. The occurrence of zearalenone was 4.63% and that of ochratoxin A was 1.85%, with the other four groups mycotoxins were below the limits of quantification. The hazard index values for the five groups’ non-carcinogenic mycotoxins were far below 1.0. The deterministic risk assessment indicated no non-carcinogenic risks for dark tea consumption in the three areas. Probabilistic estimation showed that the maximum value of 95th percentile carcinogenic risk value for the aflatoxins was 2.12 × 10⁻⁸, which is far below the acceptable carcinogenic risk level (10⁻⁶). Hereby, six groups mycotoxins in Chinese dark tea showed no observed risk concern to consumers.

To elucidate the origin of the wide-spread contaminations of plant derived commodities with various alkaloids, we employed co-cultures of pyrrolizidine alkaloid (PA) containing Senecio jacobaea plants with various alkaloid free acceptor plants. Our analyses revealed that all plants grown in the vicinity of the Senecio donor plants indeed contain significant amounts of the PAs, which previously had been synthesized in the Senecio plants. These findings illustrate that typical secondary metabolites, such as pyrrolizidine alkaloids, are commonly transferred and exchanged between living plants. In contrast to the broad spectrum of alkaloids in Senecio, in the acceptor plants nearly exclusively jacobine is accumulated. This indicates that this alkaloid is exuded specifically by the Senecio roots. Although the path of alkaloid transfer from living donor plants is not yet fully elucidated, these novel insights will extend and change our understanding of plant-plant interactions and reveal a high relevance with respect to the widespread alkaloidal contaminations of plant-derived commodities. Moreover, they could be the basis for the understanding of various so far not fully understood phenomena in cultivation of various crops, e.g. the beneficial effects of crop rotations or the co-cultivation of certain vegetables.

Polybrominated diphenyl ethers (PBDEs) are toxic chemicals widely distributed in the environment, but few studies are available on their potential toxicity to rice at metabolic level. Therefore we exposed ten rice (Oryza sativa) varieties to 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), a predominant congener of PBDEs, in hydroponic solutions with different concentrations. Two varieties that showed different biological effects to BDE-47, YY-9 and LJ-7, were screened as sensitive and tolerant varieties according to changes of morphological and physiological indicators. Metabolic research was then conducted using gas chromatography−mass spectrometry combined with diverse analyses. Results showed that LJ-7 was more active in metabolite profiles and adopted more effective antioxidant defense machinery to protect itself against oxidative damages induced by BDE-47 than YY-9. For LJ-7, the contents of 13 amino acids and 24 organic acids, especially l-glutamic acid, beta-alanine, glycolic acid and glyceric acid were up-regulated significantly which contributed to scavenging reactive oxygen species. In the treatment of 500 μg/L BDE-47, the contents of these four metabolites increased by 33.6-, 19.3-, 10.6- and 10.2-fold, respectively. The levels of most saccharides (such as d-glucose, lactulose, maltose, sucrose and d-cellobiose) also increased by 1.7–12.4 fold which promoted saccharide-related biosynthesis metabolism. Elevation of tricarboxylic acid cycle and glyoxylate and dicarboxylate metabolism enhanced energy-producing processes. Besides, the contents of secondary metabolites, chiefly polyols and glycosides increased significantly to act on defending oxidative stress induced by BDE-47. In contrast, the levels of most metabolites decreased significantly for YY-9, especially those of 13 amino acids (by 0.9%–67.1%) and 19 organic acids (by 7.8%–70.0%). The positive metabolic responses implied LJ-7 was tolerant to BDE-47, while the down-regulation of most metabolites indicated the susceptible nature of YY-9. Since metabolic change might affect the yield and quality of rice, this study can provide useful reference for rice cultivation in PBDEs-polluted areas.

Mycotoxins are secondary metabolites produced by varieties of fungi that contaminate food and feed resources and are capable of inducing a wide range of toxicity. In the current study, we investigated developmental and behavioural toxicity in zebrafish larvae after exposure to six different mycotoxins; ochratoxin A (OTA), type A trichothecenes mycotoxin (T-2 toxin), type B trichothecenes mycotoxin (deoxynivalenol - DON), and zearalenone (ZEN) and its metabolites alpha-zearalenol (α-ZOL) and beta-zearalenol (β-ZOL). Developmental defects, hatching time, and survival were monitored until 96 h post fertilisation (hpf). The EC₅₀, LC₅₀, and IC₅₀ values were calculated. Subsequently, to assess behavioural toxicity, new sets of embryos were exposed to a series of non-lethal doses within the range of environmental and/or developmental concern. Results indicated that all the tested mycotoxins were toxic, they all induced developmental defects, and with the exception of OTA, all affected hatching time. Behavioural effects were only observed following exposure to OTA and ZEN and its metabolites, α ZOL and β ZOL. These results demonstrate that mycotoxins are teratogenic and can influence behaviour in a vertebrate model.

Mycotoxin is toxic secondary metabolite formed by certain filamentous fungi. This toxic compound can enter the food chain through contamination of food (e.g., by colonization of toxigenic fungi on food). In light of the growing concerns on the health hazards posed by mycotoxins, it is desirable to develop reliable analytical tools for their detection in food products in both sensitive and efficient manner. For this purpose, the potential utility of molecularly imprinted polymers (MIPs) has been explored due to their meritful properties (e.g., large number of tailor-made binding sites, sensitive template molecules, high recognition specificity, and structure predictability). This review addresses the recent advances in the application of MIPs toward the sensing of various mycotoxins (e.g., aflatoxins and patulin) along with their fabrication strategies. Then, performance evaluation is made for various types of MIP- and non-MIP-based sensing platforms built for the listed target mycotoxins in terms of quality assurance such as limit of detection (LOD). Further, the present challenges in the MIP-based sensing application of mycotoxins are discussed along with the future outlook in this research field.

Rice paddy fields are major sources of atmospheric methane (CH₄) and nitrous oxide (N₂O). Rice variety is an important factor affecting CH₄ and N₂O emissions. However, the interactive effects of rice metabolites and microorganisms on CH₄ and N₂O emissions in paddy fields are not clearly understood. In this study, a high greenhouse gas-emitting cultivar (YL 6) and a low greenhouse gas-emitting cultivar (YY 1540) were used as experimental materials. Metabolomics was used to examine the roots, root exudates, and bulk soil metabolites. High-throughput sequencing was used to determine the microbial community composition. YY 1540 had more secondary metabolites (flavonoids and isoflavonoids) in root exudates than YL 6. It was enriched with the uncultured members of the families Gemmatimonadanceae and Rhizobiales_Incertae_Sedis in bulk soil, and genera Burkholderia-Caballeronia-Paraburkholderia, Magnetospirillum, Aeromonas, and Anaeromyxobacter in roots, contributing to increased expression of pmoA and nosZ genes and reducing CH₄ and N₂O emissions. YL 6 roots and root exudates contained higher contents of carbohydrates [e.g., 6-O- acetylarbutin and 2-(3- hydroxyphenyl) ethanol 1′-glucoside] than those of YY 1540. They were enriched with genera RBG-16-58-14 in bulk soil and Exiguobacterium, and uncultured member of the Kineosporiaceae family in roots, which contributed to increased expression of mcrA, ammonia-oxidizing archaea, ammonia-oxidizing bacteria, nirS, and nirK genes and greenhouse gas emissions. In general, these results established a link between metabolites, microorganisms, microbial functional genes, and greenhouse gas emissions. The metabolites of root exudates and roots regulated CH₄ and N₂O emissions by influencing the microbial community composition in bulk soil and roots.

Despite the broad use of lichens as biomonitors of airborne trace elements, the surface chemistry and metal adsorption parameters of these organisms are still poorly known. The current investigation is aimed at (i) quantifying the acid-base surface properties and the first-order physical-chemical parameters of Cu²⁺ and Zn²⁺ adsorption of devitalized Pseudevernia furfuracea, a lichen commonly used in biomonitoring of airborne trace elements, and (ii) comparing the results with those available for moss biomonitors. Equilibrium constants and metal-binding site concentrations were calculated with a thermodynamic model by taking into account the presence/absence of ancillary extracellular cell wall compounds, namely melanin and acetone-soluble lichen substances. An acid–base titration experiment performed in the pH range of 3–10 showed that melanised and non-melanised P. furfuracea samples have lower pHPZC (3.53–3.99) and higher metal-binding site concentrations (0.96–1.20 mmol g⁻¹) compared to that of the mosses investigated so far at the same experimental conditions. Melanin biosynthesis increased the content of carboxyl and phosphoryl groups and reduces that of amine/polyphenols. Cu²⁺ and Zn²⁺ adsorption was unaffected by the degree of melanisation while the removal of extracellular lichen substances slightly decreased Zn²⁺ adsorption. Although Cu²⁺ and Zn²⁺ adsorption parameters related to P. furfuracea surfaces were 3 times lower than in the mosses, lichen samples adsorbed the same amount of Cu²⁺ and 30% more Zn²⁺. The present study contributes in understanding the role of ancillary cell wall compounds in Cu²⁺ and Zn²⁺ adsorption in a model lichen. It also provides a first comparison between the surface physico-chemical characteristics of lichens and mosses frequently used as biomonitors of trace elements.