Concentration levels and ecological risk assessment of typical organophosphate esters in representative surface waters of a megacity.

Organophosphate esters (OPEs) have been widely used as flame retardants and plasticizers in consumer and industrial products. They have been found to have numerous exposure hazards. Recently, several OPEs have been detected in surface waters around the world, which may pose potential ecological risks to freshwater organisms. In this study, the concentration, spatial variation, and ecological risk of 15 OPEs in the Beiyun and Yongding rivers were unprecedentedly investigated by the ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and risk quotient (RQ) method. The result showed that triethyl phosphate (TEP), tri (2-chloroisopropyl) phosphate (TCPP) were the most abundant OPEs with average concentrations of 55.53 ng/L and 42.29 ng/L, respectively. The concentrations of OPEs in the Beiyun River are higher than in the Yongding River, and their levels were higher in densely populated and industrial areas. The risk assessment showed that there was insignificant from OPEs to freshwater organisms in these rivers (RQs <0.1). The risk was higher downstream than upstream, which was related to human-intensive industrial activities downstream in the Yongding River. The ecological risk of OPEs in surface waters worldwide was estimated by joint probability curves (JPCs), and the result showed that there was a moderate risk for tri (2-chloroethyl) phosphate (TCEP), a low risk for trimethyl phosphate (TMP), and insignificant for other OPEs. In addition, the QSAR-ICE-SSD model was used to calculate the hazardous concentration for 5% (HC5). This result validated the feasibility and accuracy of this model in predicting acute data of OPEs and reducing biological experiments on the toxicity of OPEs. These results revealed the ecological risk of OPEs and provided the scientific basis for environmental managers.

Toxicity mechanisms and bioavailability of copper to fish based on an adverse outcome pathway analysis.

Copper (Cu) exists in a variety of forms in different aquatic environments, and affects their bioavailability. In this study we provide a systematic review on toxicity of Cu which focuses on identifying evidence in the mechanisms of Cu toxicity, and apply an adverse outcome pathway (AOP) analysis to identify multiple potential mechanisms and their interactions of Cu toxicity to fish. This analysis process included the mechanisms of behavior toxicant, oxidative toxicant, ion regulation disruption toxicity, as well as endocrine disruption toxicity. It was found that at low levels of Cu exposure, swimming, avoid predators, locating prey and other sensory functions will be impaired, and the organism will suffer from metabolic alkalosis and respiratory acidosis following the inhibition of the carbonic anhydrase active. The main pathway of acute toxicity of Cu to fish is the inhibition of the Na+/K+-ATPase enzyme, and lead to reduced intracellular sodium absorption, as well as Cu-induced increased cell permeability, in turn resulting in increased sodium ion loss, leading to cardiovascular collapse and respiratory insufficiency. The endocrine disruption toxicity of Cu to fish caused growth inhibition and reproductive reduction. In addition, there are several key pathways of Cu toxicity that are affected by hardness (e.g., Ca2+) and intracellular DOC concentrations, including inhibiting Cu-induction, improving branchial gas exchange, altering membrane transport functions, decreasing Na+ loss, and increasing Na+ uptake. The results of the AOP analysis will provide a robust framework for future directed research on the mechanisms of Cu toxicity.

High-quality chromosome-scale de novo assembly of the Paspalum notatum 'Flugge' genome.

BACKGROUND: Paspalum notatum 'Flugge' is a diploid with 20 chromosomes (2n = 20) multi-purpose subtropical herb native to South America and has a high ecological significance. It is currently widely planted in tropical and subtropical regions. Despite the gene pool of P. notatum 'Flugge' being unearthed to a large extent in the past decade, no details about the genomic information of relevant species in Paspalum have been reported. In this study, the complete genome information of P. notatum was established and annotated through sequencing and de novo assembly of its genome. RESULTS: The latest PacBio third-generation HiFi assembly and sequencing revealed that the genome size of P. notatum 'Flugge' is 541 M. The assembly result is the higher index among the genomes of the gramineous family published so far, with a contig N50 = 52Mbp, scaffold N50 = 49Mbp, and BUSCOs = 98.1%, accounting for 98.5% of the estimated genome. Genome annotation revealed 36,511 high-confidence gene models, thus providing an important resource for future molecular breeding and evolutionary research. A comparison of the genome annotation results of P. notatum 'Flugge' with other closely related species revealed that it had a close relationship with Zea mays but not close compared to Brachypodium distachyon, Setaria viridis, Oryza sativa, Puccinellia tenuiflora, Echinochloa crusgalli. An analysis of the expansion and contraction of gene families suggested that P. notatum 'Flugge' contains gene families associated with environmental resistance, increased reproductive ability, and molecular evolution, which explained its excellent agronomic traits. CONCLUSION: This study is the first to report the high-quality chromosome-scale-based genome of P. notatum 'Flugge' assembled using the latest PacBio third-generation HiFi sequencing reads. The study provides an excellent genetic resource bank for gramineous crops and invaluable perspectives regarding the evolution of gramineous plants.

A de novo assembled high-quality chromosome-scale Trifolium pratense genome and fine-scale phylogenetic analysis.

BACKGROUND: Red clover (Trifolium pratense L.) is a diploid perennial temperate legume with 14 chromosomes (2n = 14) native to Europe and West Asia, with high nutritional and economic value. It is a very important forage grass and is widely grown in marine climates, such as the United States and Sweden. Genetic research and molecular breeding are limited by the lack of high-quality reference genomes. In this study, we used Illumina, PacBio HiFi, and Hi-C to obtain a high-quality chromosome-scale red clover genome and used genome annotation results to analyze evolutionary relationships among related species. RESULTS: The red clover genome obtained by PacBio HiFi assembly sequencing was 423 M. The assembly quality was the highest among legume genome assemblies published to date. The contig N50 was 13 Mb, scaffold N50 was 55 Mb, and BUSCO completeness was 97.9%, accounting for 92.8% of the predicted genome. Genome annotation revealed 44,588 gene models with high confidence and 52.81% repetitive elements in red clover genome. Based on a comparison of genome annotation results, red clover was closely related to Trifolium medium and distantly related to Glycine max, Vigna radiata, Medicago truncatula, and Cicer arietinum among legumes. Analyses of gene family expansions and contractions and forward gene selection revealed gene families and genes related to environmental stress resistance and energy metabolism. CONCLUSIONS: We report a high-quality de novo genome assembly for the red clover at the chromosome level, with a substantial improvement in assembly quality over those of previously published red clover genomes. These annotated gene models can provide an important resource for molecular genetic breeding and legume evolution studies. Furthermore, we analyzed the evolutionary relationships among red clover and closely related species, providing a basis for evolutionary studies of clover leaf and legumes, genomics analyses of forage grass, the improvement of agronomic traits.

General Challenges and Recommendations for the Water Quality Criteria of Endocrine Disrupting Chemicals (EDCs).

Water quality criteria (WQC) play an important role in the environmental management of pollutants in different countries or institutions. It has been found that endocrine disrupting chemicals (EDCs) can potentially alter functions of the endocrine system and consequently cause adverse effects in aquatic organisms. Therefore, the complicated modes of action and mechanisms of EDCs should be carefully considered in WQC studies. For example, the research regarding the WQC derivation of EDCs should prioritize sensitive aquatic species in consideration of the WQC derivation. Second, the chronic toxicity of EDCs should be of utmost concern. In addition, the appropriate effects and endpoints of EDCs should be carefully selected for the WQC derivation. Moreover, it was pointed out that some new methods should be taken into consideration in the WQC studies of EDCs in the near future.

Technical study on national mandatory guideline for deriving water quality criteria for the protection of freshwater aquatic organisms in China.

Water quality criteria are the basis for formulating environmental water quality standards, and are also an important part of environmental water protection and environmental management programs. The current study focused on a systematic discussion of the current research progress of water quality criteria theories and methodology for aquatic organisms both in China and internationally. This study also successfully pointed out key scientific issues which should be considered in the determination of water quality criteria guidelines from the following perspectives for a national strategy: the selection of pollutants; data collection and screening; species selection; water quality criteria derivation methods, and so on. For the first time, this study systematically introduced technology for the determination of water quality criteria guidelines for protecting aquatic organisms which was suitable for China's regional characteristics and national conditions. Furthermore, this study pointed out the key research directions which should be considered in the future construction of China's environmental criteria and management systems, in order to provide technical support for environmental protection and management projects.

Influence of Hardness and Dissolved Organic Carbon on the Acute Toxicity of Copper to Zebrafish (Danio rerio) at Different Life Stages.

Copper (Cu) bioavailability varies under water conditions. In the present study, the whole life of zebrafish was divided into three different life stages (larvae, juvenile and adult) based on the growth curve, then the influences of water hardness and dissolved organic carbon (DOC) concentration on the acute toxicity of zebrafish were respectively investigated. The results indicated that the life stages had significant effects on Cu toxicity. The larvae stage was less sensitive to Cu than both the juvenile and adult stages. With the increase of water hardness, the toxicity of Cu on zebrafish was decreased, a linear relationship was observed between water hardness and Cu toxicity, and the same was true for DOC concentration. The results showed that taking the 24 days juvenile zebrafish to study the water quality criteria of Cu was stable, sensitive and economical.

Water temperature governs organophosphate ester dynamics in the aquatic food chain of Poyang Lake.

Organophosphate esters (OPEs) are increasingly recognized as pervasive environmental contaminants, primarily from their extensive application in flame retardants and plasticizers. Despite their widespread presence, the intricacies of OPE bioaccumulation within aquatic ecosystems remain poorly understood, particularly the environmental determinants influencing their distribution and the bioaccumulation dynamics across aquatic food chains. Here we show that water temperature plays a crucial role in modulating the dispersion of OPE in the aquatic environment of Poyang Lake. We quantified OPE concentrations across various matrices, uncovering levels ranging from 0.198 to 912.622 ng L-1 in water, 0.013-493.36 ng per g dry weight (dw) in sediment, 0.026-41.92 ng per g wet weight (ww) in plankton, 0.13-2100.72 ng per g dw in benthic invertebrates, and 0.31-3956.49 ng per g dw in wild fish, highlighting a pronounced bioaccumulation gradient. Notably, the intestines emerged as the principal site for OPE absorption, displaying the highest concentrations among the seven tissues examined. Among the various OPEs, tris(chloroethyl) phosphate was distinguished by its significant bioaccumulation potential within the aquatic food web, suggesting a need for heightened scrutiny. The propensity for OPE accumulation was markedly higher in benthic invertebrates than wild fish, indicating a differential vulnerability within aquatic biota. This study lays a foundational basis for the risk assessment of OPEs as emerging contaminants and underscores the imperative to prioritize the examination of bioaccumulation effects, particularly in benthic invertebrates, to inform future environmental safeguarding strategies.

Freshwater Water-Quality Criteria for Chloride and Guidance for the Revision of the Water-Quality Standard in China.

The chloride in water frequently exceeds the standard; directly quoting foreign water-quality criteria (WQC) or standards will inevitably reduce the scientific value of the water-quality standard (WQS) in China. Additionally, this may lead to the under- or overprotection of water bodies. This study summarized the sources, distribution, pollution status, and hazards of chloride in China's water bodies. Additionally, we compared and analyzed the basis for setting WQS limits for chloride in China; we systematically analyzed the basis for setting the WQC for chloride in foreign countries, especially the United States. Finally, we collected and screened data on the toxicity of chloride to aquatic organisms; we also used the species sensitivity distribution (SSD) method to derive the WQC value for chloride, which is 187.5 mg·L-1. We put forward a recommended value for freshwater WQS for chloride in China: less than 200 mg·L-1. The study of a freshwater WQC for chloride is not only a key point of environmental research, but also an urgent demand to ensure water ecological protection in China. The results of this study are of great significance for the environmental management of chloride, protection of aquatic organisms, and risk assessment, especially for the revision of WQSs.

Distribution and Characterization of Typical Antibiotics in Water Bodies of the Yellow River Estuary and Their Ecological Risks.

A total of 34 antibiotics from five major classes of antibiotics, including macrolides, sulfonamides, quinolones, tetracyclines and chloramphenicol, were considered as contaminants, considering the Yellow River Estuary as the study area. The distribution, sources and ecological risks of typical antibiotics in the Yellow River Estuary were investigated using an optimized solid-phase extraction pre-treatment and an Agilent 6410B tandem triple-quadrupole liquid chromatography-mass spectrometer for antibiotic detection. The results show that antibiotics were widely present in the water bodies of the Yellow River Estuary, with 14 antibiotics detected to varying degrees, including a high detection rate for lincomycin hydrochloride. Farming wastewater and domestic sewage were the primary sources of antibiotics in the Yellow River Estuary. The distribution characteristics of antibiotics in the study area were linked to the development of farming and social activities. The ecological risk evaluation of 14 antibiotics in the Yellow River Estuary watershed showed that clarithromycin and doxycycline hydrochloride were present at medium-risk levels, and lincomycin hydrochloride, sulfamethoxazole, methomyl, oxifloxacin, enrofloxacin, sulfadiazine, roxithromycin, sulfapyridine, sulfadiazine and ciprofloxacin were present at low-risk levels in the samples collected from water bodies of the Yellow River Estuary. This study provides novel, beneficial information for the assessment of the ecological risk presented by antibiotics in the Yellow River Estuary water bodies and provides a scientific basis for future antibiotic pollution control in the Yellow River Basin.

Insights into the geographical distribution, bioaccumulation characteristics, and ecological risks of organophosphate esters.

Organophosphate esters (OPEs), as flame retardants and plasticizers, have been numerously explored regarding the occurrence and ecotoxicology. Given their toxicity, persistency and bio-accumulative potential, however, they may pose negative effects on ecosystems, regarding which is a growing global concern. Accordingly, the present review systematically analyses the recent literature to (1) elucidate their worldwide distribution, bioaccumulation, and biomagnification potential, (2) determine their interim water quality criteria (i.e., effect thresholds), and (3) preliminarily assess the ecological risks for 32 OPEs in aquatic ecosystems. The results showed that the spatiotemporal distribution of OPEs was geographically specific and closely related to human activities (i.e., megacities), especially halogenated-OPEs. We also found that precipitation of airborne particulates could affect the concentrations of OPEs in soil, and there was a positive correlation between the bioaccumulation and hydrophobicity of OPEs. Tris(2-ethylhexyl) phosphate may exhibit high bioaccumulation in aquatic organisms. A substantial difference was found among interim water quality criteria for OPEs, partly attributable to the variation of their available toxicity data. Tris(phenyl) phosphate (TPHP) and tris(1,3-dichloroisopropyl) phosphate with the lowest predicted no-effect concentration showed the strongest toxicity of growth and reproduction. Through the application of the risk quotient and joint probability curve, TPHP and tris(chloroethyl) phosphate tended to pose moderate risks, which should receive more attention for risk management. Future research should focus on knowledge gaps in the mechanism of biomagnification, derivation of water quality criteria, and more precise assessment of ecological risks for OPEs.

The Distribution Characteristics and Ecological Risks of Alkylphenols and the Relationships between Alkylphenols and Different Types of Land Use.

In this study, the spatial distribution characteristics of nine alkylphenols (APs) in the Yongding River and Beiyun River were analyzed. The differences in the concentrations and spatial distribution patterns of nine APs were systematically evaluated using principal component analysis (PCA). The relationships between the concentration distribution patterns and the risks associated with nine APs were investigated under various categories of land use conditions in the region. The results demonstrated that the APs were widely present in both rivers, and the pollution risks associated with the APs were more severe in the Yongding River than in the Beiyun River. The results show that the contamination risks associated with 4-NP were the most serious in the two rivers, with detection percentages of 100% and 96.3%, respectively. In the Yongding River, the APs showed a tendency of low concentration levels in the upper reaches and high levels in the middle and lower regions. Meanwhile, the overall concentration levels of the APs in the Beiyun River were relatively high. However, despite the differences between the upper and middle regions of the Yongding River, the distribution pattern of the APs in the Beiyun River was basically stable. The concentration levels and risk quotient of the APs were negatively correlated with the vegetation cover land use type and positively correlated with the cropland and unused land use types within 500 m, 1 km, and 2 km. The purpose of this study was to provide theoretical data support and a basis for AP pollution risk evaluations in the Yongding River and Beiyun River.

Screening of universal DNA barcodes for identifying grass species of Gramineae.

There is currently international interest in applying DNA barcoding as a tool for plant species discrimination and identification. In this study, we evaluated the utility of four candidate plant DNA barcoding regions [rbcL, matK, trnL-F, and internal transcribed spacer (ITS)] in seven genera of Gramineae including Agropyron, Bromus, Elymus, Elytrigia, Festuca, Leymus, and Lolium. Fourteen accessions were analyzed, and matK and ITS showed the highest species, subspecies, and variety discriminatory power, each resolving 11 accessions. Species discrimination using rbcL and trnL-F was lower, resolving 7 and 8 accessions, respectively. Subspecies and variety discrimination using rbcL and trnL-F could not identify 4 accessions of Agropyron. A technical system can be established using the proposed DNA barcode to rapidly and reliably identify the seven genera of Gramineae. This study serves as a "useful reference" for identifying the genetic diversity of grass germplasm resources. DNA barcoding can be utilized to uncover the relatives of different species within the same family or between different families. It can also be used to determine the related groups of important herbage, turfgrass, and crops and provide crucial background information for discovering excellent genes and improving existing crop varieties.

Organophosphate esters cause thyroid dysfunction via multiple signaling pathways in zebrafish brain.

Organophosphate esters (OPEs) are widespread in various environmental media, and can disrupt thyroid endocrine signaling pathways. Mechanisms by which OPEs disrupt thyroid hormone (TH) signal transduction are not fully understood. Here, we present in vivo-in vitro-in silico evidence establishing OPEs as environmental THs competitively entering the brain to inhibit growth of zebrafish via multiple signaling pathways. OPEs can bind to transthyretin (TTR) and thyroxine-binding globulin, thereby affecting the transport of TH in the blood, and to the brain by TTR through the blood-brain barrier. When GH3 cells were exposed to OPEs, cell proliferation was significantly inhibited given that OPEs are competitive inhibitors of TH. Cresyl diphenyl phosphate was shown to be an effective antagonist of TH. Chronic exposure to OPEs significantly inhibited the growth of zebrafish by interfering with thyroperoxidase and thyroglobulin to inhibit TH synthesis. Based on comparisons of modulations of gene expression with the Gene Ontology and Kyoto Encyclopedia of Genes and Genomes databases, signaling pathways related to thyroid endocrine functions, such as receptor-ligand binding and regulation of hormone levels, were identified as being affected by exposure to OPEs. Effects were also associated with the biosynthesis and metabolism of lipids, and neuroactive ligand-receptor interactions. These findings provide a comprehensive understanding of the mechanisms by which OPEs disrupt thyroid pathways in zebrafish.

The potential connections of adverse outcome pathways with the hazard identifications of typical organophosphate esters based on toxicity mechanisms.

Following the world-wide ban of brominated flame retardants (BFRs), organophosphate esters (OPEs), which could potentially affect human health and ecosystem safety, have been frequently detected in various environmental media. However, the knowledge regarding the underlying toxicity effects of OPEs remains limited. In order to address these issues, this study reviewed the related reports which have been published in recent years. This analysis process included 12 OPEs, 10 model organisms, and 15 cell lines, which were used to systematically examine the mechanisms of endocrine disruption, neurotoxicity, hepatotoxicity, and cardiotoxicity, as well as reproductive and developmental toxicity. Subsequently, an adverse outcome pathway (AOP) framework of the toxicological effects of OPEs was built. The results demonstrated that multiple different pathways may lead to a single same adverse outcome (AO), and there was a certain degree of correlation among the different AOs. It was found that among all the 12 OPEs, tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) may potentially be the most toxic. In addition, rather than the parent chemicals, the metabolites of OPEs may also have different degrees of toxicity effects on aquatic organisms and humans. Overall, the results of the present study also suggested that an AOP framework should be built via fully utilizing the existing toxicity data of OPEs based on in vivo-in vitro-in silico to completely and deeply understand the toxic mechanisms of OPEs. This improved knowledge could then provide a theoretical basis for ecological risk assessments and water quality criteria research in the near future.

In vitro metabolic kinetics of cresyl diphenyl phosphate (CDP) in liver microsomes of crucian carp (Carassius carassius).

Cresyl diphenyl phosphate (CDP), as a kind of aryl substituted organophosphate esters (OPEs), is commonly used as emerging flame retardants and plasticizers detected in environmental media. Due to the accumulation of CDP in organisms, it is very important to discover the toxicological mechanism and metabolic process of CDP. Hence, liver microsomes of crucian carps (Carassius carassius) were prepared for in vitro metabolism kinetics assay to estimate metabolism rates of CDP. After 140 min incubation, the depletion of CDP accounted for 58.1%-77.1% (expect 0.5 and 2 µM) of the administrated concentrations. The depletion rates were best fitted to the Michaelis-Menten model (R2 = 0.995), where maximum velocity (Vmax) and Michaelis-Menten constant (Km) were 12,700 ± 2120 pmol min-1·mg-1 protein and 1030 ± 212 µM, respectively. Moreover, the in vitro hepatic clearance (CLint) of CDP was 12.3 µL min-1·mg-1 protein. Log Kow and bioconcentration factor (BCF) of aryl-OPEs were both higher than those of alkyl- and chlorinated-OPEs, indicating that CDP may easily accumulate in aquatic organisms. The results made clear that the metabolism rate of CDP was greater than those of other OPEs detected in liver microsomes in previous research. This paper was first of its kind to comprehensively investigate the in vitro metabolic kinetics of CDP in fish liver microsomes. The present study might provide useful information to understand the environmental fate and metabolic processes of these kinds of substances, and also provide a theoretical basis for the ecological risk assessment of emerging contaminants.

The toxicity effects and mechanisms of tris(1,3-dichloro-2-propyl) phosphate (TDCPP) and its ecological risk assessment for the protection of freshwater organisms.

Tris (1,3-dichloro-2-propyl) phosphate (TDCPP) is a type halogenated organophosphate flame retardants (OPFRs), which has been identified as contaminants of emerging concern (CECs). The use and production of OPFRs began to increase gradually when brominated flame retardants (BFRs) were banned. Halogenated OPFRs, especially TDCPP have been considered to lead to mutagenicity and carcinogenesis and major concerns have been raised regarding their toxicity. In this study, the toxicity effects and mechanisms of TDCPP were summarized and ecological risk assessment was made regarding its potential impact on freshwater organisms. TDCPP has been widely detected in ecosystems throughout the world, with observed toxicity effects on both humans and freshwater organisms. Inhalation of the dust was found to be the main exposure for humans. TDCPP could be metabolized in the human body, and medium stability was achieved in human body with the main metabolite BDCPP. Aside from mutagenicity and carcinogenesis, TDCPP was also found to have the potential for endocrine disruption and impairing the human reproductive system. Furthermore, this study reviewed the results of previous toxicity experiments, including acute toxicity, growth and development toxicity, neurotoxicity, and hepatotoxicity in freshwater organisms. Risk assessment was made using the safety threshold method by comparing the toxicity data with the exposure data in freshwater. HC5 (hazardous concentration for 5% of organisms) derived based on traditional endpoints of acute toxicity LC50 (median lethal concentration) or EC50 (concentration for 50% of maximal effect) was 877 µg/L. This value was much higher than the exposure concentration levels in the surface water with EXD90 (exposure data with cumulative probability 90%) of 65.22 ng/L. However, based on the growth and development toxicity data, the derived HC5 was 33.33 ng/L and the calculated MOS (margin of safety) was below 1. Therefore, the results validated the fact that the ecological risk of TDCPP could not be neglected for its growth and development toxicity.