Insights into the occurrence, spatial distribution, and ecological implications of organophosphate triesters in surface sediments from polluted urban rivers across China.

Organophosphate triesters (tri-OPEs) are a kind of widespread contaminants in the world, particularly in China, which is a major producer and user of tri-OPEs. However, tri-OPE pollution in urban river sediments in China remains unclear. In current work, we carried out the first nationwide investigation to comprehensively monitor 10 conventional and five emerging tri-OPEs in sediments of 173 black-odorous urban rivers throughout China. Concentrations of 10 conventional and five emerging tri-OPEs were 3.8-1240 ng/g dw (mean: 253 ng/g dw) and 0.21-1107 ng/g dw (68 ng/g dw), respectively, and significantly differed among the cities sampled but generally decreased from Northeast and East China to Central and West China. These spatial patterns suggest that tri-OPE pollution was mainly from local sources and was controlled by the industrial and economic development levels in these four areas, as indicated by the significant correlations between tri-OPE concentrations and gross domestic production, gross industrial output, and daily wastewater treatment capacity. Although the tri-OPE composition varied spatially at different sites, which indicated different tri-OPE input patterns, it was commonly dominated by tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, and tris(1-chloro-2-propyl) phosphate (conventional tri-OPEs) and bisphenol A-bis(diphenyl phosphate) and isodecyl diphenyl phosphate (emerging tri-OPEs). A risk assessment indicated that tri-OPEs in most sampling sediments had a low to moderate risk to aquatic organisms.

Occurrence, spatial distribution, and risk assessment of short- and medium-chain chlorinated paraffins in sediment from black-odorous rivers across China.

Chlorinated paraffins (CPs) were massively produced for varied industrial purposes, of which improper handling and consequent environmental release resulted in worldwide contamination. The present study investigated the occurrence and spatial distribution of short- and medium-chain chlorinated paraffins (SCCP/MCCPs) in 171 sediment samples from black-odorous urban rivers across China. Total SCCP and MCCP concentrations ranged from 8.3 to 9.4 × 104 (median: 1.1 × 103) ng/g dw, and from not-detected-value to 1.0 × 106 (median: 1.3 × 104) ng/g dw, respectively. No clear spatial distribution of SCCPs and MCCPs was observed since black-odorous urban rivers were polluted by point-sources of the SCCP/MCCPs. Significant positive correlations were identified between SCCP/MCCPs and total organic carbon, and between SCCP/MCCPs and other persistent organic matter, including polybrominated diethyl ethers, polychlorinated biphenyls, antibiotics, and plasticizers. The average ratios of MCCPs to SCCPs in most samples were divided into 11 and 16, implying the manufacturing and use of at least two types of CP technical mixtures in China. The composition of SCCP/MCCPs were similar to that in their commercial products. Ecological risk assessments by two approaches, including the Federal Environmental Quality Guidelines and Risk Quotient, both revealed that SCCP/MCCP in surface sediments confer an ecological risk. ENVIRONMENTAL IMPLICATION: SCCPs and MCCPs can be considered "hazardous materials" because of their massive production and their potential persistence, long-distance transfer, bioaccumulation potential, and toxicity. This research conducted a comprehensive study on SCCP/MCCP in black-odorous urban river sediments across China and revealed their environmental risk, which may improve understanding of SCCP/MCCP contamination characteristics.

Cryptocaryone induces apoptosis in human hepatocellular carcinoma cells by inhibiting aerobic glycolysis through Akt and c-Src signaling pathways.

Hepatocellular carcinoma (HCC) is the most common form of liver cancer, with the second highest mortality rate in all cancer. Energy reprogramming is one of the hallmarks of cancer, and emerging evidence showed that targeting glycolysis is a promising strategy for HCC treatment. Cryptocaryone has been shown to display promising anti-cancer activity against numerous types of cancer. Previous study also indicated that cryptocaryone induces cytotoxicity by inhibiting glucose transport in cancer cells, but the detailed mechanism still needs to be elucidated. Therefore, this study aimed to investigate the relationship between the anti-cancer effect and glycolytic metabolism of cryptocaryone in human HCC cells. In this study, we found that cryptocaryone potently induced growth inhibition by apoptotic cell death in HCC cells. Cryptocaryone also suppressed the ATP synthesis, lactate production and glycolytic capacity of HCC cells. Mechanistic investigations showed that phosphorylation of Akt and c-Src, as well as the expression of HK1 were impeded by cryptocaryone. Moreover, cryptocaryone markedly increased the expression level of transcription factor FoxO1. Importantly, clinical database analysis confirmed the negative correlation between HK1 and FoxO1. High expression levels of HK-1 were positively correlated with poorer survival in patients with HCCs. These results suggest that cryptocaryone may promote cell apoptosis by inhibiting FoxO1-mediated aerobic glycolysis through Akt and c-Src signaling cascades in human HCC cells. This is the first study to indicate that cryptocaryone exerts anti-cancer property against human HCC cells. Cryptocaryone is a potential natural product worthy of further development into a promising candidate for HCC treatment.

Tissue-Specific Distribution of Legacy and Emerging Organophosphorus Flame Retardants and Plasticizers in Frogs.

Five types of tissues, including the liver, kidney, intestine, lung, and heart, were collected from black-spotted frogs and bullfrogs to study the tissue-specific accumulation of organophosphorus flame retardants (PFRs) and plasticizers. Thirteen PFRs and nine plasticizers were detected, with average total concentrations of 1.4-13 ng/g ww and 858-5503 ng/g ww in black-spotted frogs, 3.6-46 ng/g ww and 355-3504 ng/g ww in bullfrogs. Significant differences in pollutant concentrations among different tissues in the two frog species were found, indicating the specific selectivity distribution of PFRs and plasticizers. Overall, liver tissues exhibited significantly higher pollutant concentrations. The pollutant concentration ratios of other tissue to the sum of liver tissue and other tissues (OLR, Cother/(Cother + Cliver)) corresponding to male frogs were significantly greater than those of females, suggesting that male frogs could have higher metabolic potentials for PFRs and plasticizers. No obvious correlations between OLR and log KOW were found, indicating that the other factors (e.g., bioaccumulation pathway and metabolism) besides lipophicity could influence the deposition of PFRs and plasticizers in frog livers. Different parental transfer patterns for PFRs and plasticizers were observed in frogs when using different tissues as parental tissues. Moreover, the liver tissues had similar parental transfer mechanism with muscle tissues.

Legacy and alternative plasticizers in surface sediment of black-odorous urban rivers across China: Occurrence, spatial distribution, and ecological risk assessment.

In this study, surface sediment samples from 173 black-odorous urban rivers in 74 cities of China were investigated regarding the occurrence, spatial distribution, and ecological risk of legacy phthalates (LPs) and alternative plasticizers (APs). The total concentrations of Σ7LPs and Σ6APs ranged from 0.0035 to 522 µg/g dw (median: 33 µg/g dw; mean: 60 µg/g dw) and from 0.0015 to 16 µg/g dw (median: 16 µg/g dw; mean: 2.2 µg/g dw), respectively. Di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DnBP), and di-iso-butyl phthalate (DiBP) were the dominant LPs, and di-iso-decyl phthalate and di-iso-nonylcyclohexane-1,2-dicarboxylate were the dominant APs. The concentrations and compositions of the LPs and APs varied among different sites and regions, implying location-specific use or production of LPs and APs. The pollutant concentrations in southern and central China were higher than those in northern China. Among the seven regions, Northwest China had the lowest concentrations of LPs and APs. This could be related to industry development level, municipal facilities, and population density. Total organic carbon (TOC) was significantly and positively correlated with the pollutant concentrations, implying that TOC could be an important influencing factor for the distribution of LPs and APs in sediments. The risk quotients of DiBP and DnBP in almost all sediment samples were above 1, indicating the high ecological risks to aquatic organisms. Nevertheless, DEHP, di-methyl phthalate, di-ethyl phthalate, and di-n-octyl phthalate showed low or moderate ecological risks for most sampling sites.

RGD4C peptide mediates anti-p21Ras scFv entry into tumor cells and produces an inhibitory effect on the human colon cancer cell line SW480.

BACKGROUND: We prepared an anti-p21Ras scFv which could specifically bind with mutant and wild-type p21Ras. However, it cannot penetrate the cell membrane, which prevents it from binding to p21Ras in the cytoplasm. Here, the RGD4C peptide was used to mediate the scFv penetration into tumor cells and produce antitumor effects. METHODS: RGD4C-EGFP and RGD4C-p21Ras-scFv recombinant expression plasmids were constructed to express fusion proteins in E. coli, then the fusion proteins were purified with HisPur Ni-NTA. RGD4C-EGFP was used as reporter to test the factors affecting RGD4C penetration into tumor cell. The immunoreactivity of RGD4C-p21Ras-scFv toward p21Ras was identified by ELISA and western blotting. The ability of RGD4C-p21Ras-scFv to penetrate SW480 cells and colocalization with Ras protein was detected by immunocytochemistry and immunofluorescence. The antitumor activity of the RGD4C-p21Ras-scFv was assessed with the MTT, TUNEL, colony formation and cell migration assays. Chloroquine (CQ) was used an endosomal escape enhancing agent to enhance endosomal escape of RGD4C-scFv. RESULTS: RGD4C-p21Ras-scFv fusion protein were successfully expressed and purified. We found that the RGD4C fusion protein could penetrate into tumor cells, but the tumor cell entry of was time and concentration dependent. Endocytosis inhibitors and a low temperature inhibited RGD4C fusion protein endocytosis into cells. The change of the cell membrane potential did not affect penetrability. RGD4C-p21Ras-scFv could penetrate SW480 cells, effectively inhibit the growth, proliferation and migration of SW480 cells and promote this cells apoptosis. In addition, chloroquine (CQ) could increase endosomal escape and improve antitumor activity of RGD4C-scFv in SW480 cells. CONCLUSION: The RGD4C peptide can mediate anti-p21Ras scFv entry into SW480 cells and produce an inhibitory effect, which indicates that RGD4C-p21Ras-scFv may be a potential therapeutic antibody for the treatment of ras-driven cancers.

Legacy and emerging organophosphorus flame retardants and plasticizers in frogs: Sex difference and parental transfer.

Black-spotted frogs and bullfrogs from an e-waste polluted area were collected and examined for legacy and emerging organophosphorus flame retardants (PFRs) and plasticizers. Total concentrations of PFRs and plasticizers were 0.62-15 ng/g wet weight (ww) and 316-4904 ng/g ww in muscles, 2.2-59 ng/g ww and 127-5757 ng/g ww in eggs and gonads, and 1.2-15 ng/g ww and 51-1510 ng/g ww in oviducts, respectively. For muscle tissues, concentrations of ∑PFRs, triethyl phosphate, tris-(2-chloroethyl) phosphate, and tris-(chloro-2-propyl) phosphate were significantly higher in the males than females (p < 0.05). However, for reproductive tissues, eggs exhibited higher levels of those contaminants than gonads (p < 0.05). No significant sex difference in levels of plasticizers was observed in muscles. In contrast, levels for (2-ethylhexyl) phthalate, di-n-butyl phthalate, and di-iso-butyl phthalate in gonads were significantly higher than those in eggs (p < 0.05). Significantly negative linear correlations between maternal transfer ratios and log KOW were found in female frogs. Paternal transfer potentials were first significantly and positively correlated to log KOW (<6) and then decreased afterward in the males. These results indicated that parental transfer was answer for the sex-specific accumulation of PFRs and plasticizers in frogs.

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Canopy nitrogen content in wheat is a key indicator of wheat grain yield and quality. When using remote sensing technology to predict wheat canopy nitrogen content, a hyperspectral mode with high adaptability and high accuracy is needed to improve the inversion efficiency. We developed a new three-band spectral vegetation index (NEW-NDRE) by combining a two-band spectral index NDRE and the spectral reflectance at 550 nm based on field data collected from different sites, years, with different varieties and nitrogen levels and at multiple growth stages. The NEW-NDRE was compared with 11 traditional spectral vegetation indices in terms of wheat canopy nitrogen content inversion. NEW-NDRE and three traditional indices (NDRE, NDDA and RI-1dB) all closely correlated with wheat canopy nitrogen content. NEW-NDRE displayed the highest correlation with wheat canopy nitrogen content at early grain filling stage, with a coefficient (R2) of 0.9 and a root mean squared error (RMSE) of 0.4. The inversion model developed with the NEW-NDRE was validated with an independent dataset. The relative error (RE) of the model was 9.3%, which was significantly lower than that of NDRE, NDDA and RI-1dB. Generally, NEW-NDRE is a more robust index for wheat canopy nitrogen content inversion than traditional indices through eliminating environmental limitation, and it could be used as a new tool for precise fertilizer application.

Characterizing the Influence of Metabolism on the Halogenated Organic Contaminant Biomagnification in Two Artificial Food Chains Using Compound- and Enantiomer-Specific Stable Carbon Isotope Analysis.

Two artificial food chains, food tiger barb-oscar fish and food tiger barb-redtail catfish, were established in the laboratory. The species-specific biotransformation of ortho, para'-dichlorodiphenyltrichloroethane, 12 polychlorinated biphenyl, and five polybrominated diphenyl ether congeners were characterized by measuring the compound- and enantiomer-specific stable carbon isotope composition (δ13C), enantiomeric fraction of the chiral chemicals, and metabolites in the fish. Compound- and enantiomer-specific biotransformations were revealed by the alteration of δ13C and EF in both predator fish species. Significant correlations between the carbon stable isotope signatures and the depuration rates and biomagnification factors (BMF) were observed. Chemicals that exhibited changes in δ13C during the experiment have higher kd and lower BMF values than those with unchanged δ13C. Specifically, the difference between the predicted BMF based on the log Kow and the measured BMF, ΔBMF, was significantly positively and linearly correlated to the change in the δ13C (expressed by Δδ13C/δ13Cinitial, the percentage of Δδ13C: δ13Cending-δ13Cinitial to the initial δ13Cinitial) in both food chains. These results indicated that the impact of metabolism on the bioaccumulation potential of organic contaminants can be predicted by the stable carbon isotope fractionation of chemicals in the fish.

Level changes and human dietary exposure assessment of halogenated flame retardant levels in free-range chicken eggs: A case study of a former e-waste recycling site, South China.

To assess the impacts of e-waste regulations on environmental pollution, we built on a previous study from 2010 to investigate the levels and human dietary exposure of halogenated flame retardants (HFRs) in free-range chicken eggs from Baihe village in 2013 and 2016. The concentrations of PBDEs, PBBs, HBCDs, and DBDPE showed a significant decrease (p<0.05) from 2010 to 2013/2016, suggesting the efficacy of regulatory policies. The relative contribution of BDE209 were higher in 2013 and 2016 than in 2010, accounting for 67.8%, 61.4%, and 27.7%, respectively. The concentration ratios of PBB209:PBB153 were much lower in 2013 (1.51) and 2016 (1.32) than in 2010 (29.5). These observed different profiles likely due to the different environmental behaviors of HFRs (e.g. the different atmospheric migration abilities of PBDE congeners and degradation of PBB209). Our exposure estimates suggested high dietary intake of HFRs via home-produced eggs. As for PBDEs, considering the worst situation (highly polluted eggs were consumed), the margin of exposure (MOE) of BDE99 for both adults and children were 1.5 and 0.3 in 2013, and 1.1 and 0.2 in 2016, respectively, which were below 2.5. According to the CONTAM panel, an MOE larger than 2.5 indicates no health concern. Therefore, these MOE values represent a significant potential health concern due to the adverse impacts of PBDEs on human neurodevelopment and fertility.

Determination of organophosphorus flame retardants in fish by freezing-lipid precipitation, solid-phase extraction and gas chromatography-mass spectrometry.

An analytical method has been developed for measuring 12 organophosphorus flame retardants (PFRs) in fish tissue samples. After the Soxhlet extraction of PFRs with dichloromethane. The experimental parameters of the clean-up were systematically optimized. Methanol was found to be a more effective solvent than acetonitrile used in freezing-lipid precipitation. Methanol (5%) in ultrapure water, was finally selected to perform solid-phase extraction (SPE, Oasis HLB cartridge), with mean lipid removal efficiency of 94% after freezing-lipid precipitation. Further purification followed by 200mg of Z-Sep and C18 dispersant to eliminate the remaining interferences. Quantification was performed using gas chromatography-mass spectrometry in selective ion monitoring mode. The recovery, precision, and the method detection limits (MDLs) were verified by spiking experiments. All chemicals except triethyl phosphate (TEP) showed satisfactory recoveries in the range of 73-107% and 56-108% in the spiked blanks samples and spiked fish tissue samples, respectively. MDLs for PFRs in the biological samples ranged from 0.004 to 0.059ng/g. The proposed method successfully applied to the determination of PFRs in real fish samples with recoveries of four internal standards varying from 75 to 97%. The results demonstrated that the proposed method is highly effective for analyzing PFRs in fish samples.

Stereoselective bioaccumulation of syn- and anti-Dechlorane plus isomers in different tissues of common carp (Cyprinus carpio).

Common carps (Cyprinus carpio) were exposed to syn- and anti-Dechlorane Plus (DP) isomers to investigate absorption, tissue distribution, and stereoselective bioaccumulation of DP isomers. The absorption efficiencies of anti-DP in the gastrointestinal system were higher than those of syn-DP. A linear accumulation was found for both isomers in all fish tissues except for serum; and the liver and gill exhibited the highest and lowest DP assimilation efficiency, respectively. The elimination of DP isomers in all tissues followed first-order kinetics, with the fastest depuration rate occurring in the liver and serum. The biomagnification factors (BMFs) of both isomers were less than one in all tissues, except for serum. Anti-DP was preferably accumulated in the liver, gill, and serum, whereas syn-DP was selectively accumulated in the carcass and gastrointestinal tract. As a whole, fish did not show selective accumulation of the syn- or anti-DP isomer in the uptake stage, whereas a selective accumulation of syn-DP in fish was observed during the depuration period, which could be due to a selective excretion of anti-DP. Metabolism cannot be ruled out as a possible reason considering the high fanti values and the high elimination rate of DPs in the liver.