Metabolic perturbation and oxidative damage induced by tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and tris(2-ethylhexyl) phosphate (TEHP) on Escherichia coli through integrative analyses of metabolome.

Organophosphate esters (OPEs) are one of the emerging environmental threats, causing the hazard to ecosystem safety and human health. Yet, the toxic effects and metabolic response mechanism after Escherichia coli (E.coli) exposed to TDCIPP and TEHP is inconclusive. Herein, the levels of SOD and CAT were elevated in a concentration-dependent manner, accompanied with the increase of MDA contents, signifying the activation of antioxidant response and occurrence of lipid peroxidation. Oxidative damage mediated by excessive accumulation of ROS decreased membrane potential and inhibited membrane protein synthesis, causing membrane protein dysfunction. Integrative analyses of GC-MS and LC-MS based metabolomics evinced that significant perturbation to the carbohydrate metabolism, nucleotide metabolism, lipids metabolism, amino acid metabolism, organic acids metabolism were induced following exposure to TDCIPP and TEHP in E.coli, resulting in metabolic reprogramming. Additionally, metabolites including PE(16:1(5Z)/15:0), PA(17:0/15:1(9Z)), PC(20:2(11Z,14Z)/12:0), LysoPC(18:3(6Z,9Z,12Z)/0:0) were significantly upregulated, manifesting that cell membrane protective molecule was afforded by these differential metabolites to improve permeability and fluidity. Overall, current findings generate new insights into the molecular toxicity mechanism by which E.coli respond to TDCIPP and TEHP stress and supply valuable information for potential ecological risks of OPEs on aquatic ecosystems.

Global responses to tris(1-chloro-2-propyl) phosphate and tris(2-butoxyethyl) phosphate in Escherichia coli: Evidences from biomarkers, and metabolic disturbance using GC-MS and LC-MS metabolomics analyses.

Tris(1-chloro-2-propyl) phosphate (TCPP) and tris(2-butoxyethyl) phosphate (TBEP) as pollutants of emerging concern have aroused the rising attention due to their potential risks on aquatic ecosystem and public health. Nevertheless, there is a lack of toxicological mechanisms exploration of TCPP and TBEP at molecular levels. Herein, the toxicity effects and molecular mechanism of them were fully researched and summarized on Escherichia coli (E.coli). Acute exposure to them significantly activated antioxidant defense system and caused lipid peroxidation, as proved by the changes of antioxidant enzymes and MDA. The ROS overload resulted in the drop of membrane potential as well as the downregulated synthesis of ATPase, endorsing that E. coli cytotoxicity was ascribed to oxidative stress damage induced by TCPP and TBEP. The combination of GC-MS and LC-MS based metabolomics validated that TCPP and TBEP induced metabolic reprogramming in E.coli. More specifically, the responsive metabolites in carbohydrate metabolism, lipids metabolism, nucleotide metabolism, amino acid metabolism, and organic acids metabolism were significantly disturbed by TCPP and TBEP, confirming the negative effects on metabolic functions and key bioprocesses. Additionally, several biomarkers including PE(16:1(5Z)/15:0), PA(17:1(9Z)/18:2(9Z,12Z)), PE(19:1(9Z)/0:0), and LysoPE(0:0/18:1(11Z)) were remarkably upregulated, verifying that the protection of cellular membrane was conducted by regulating the expression of lipids-associated metabolites. Collectively, this work sheds new light on the potential molecular toxicity mechanism of TCPP and TBEP on aquatic organisms, and these findings using GC-MS and LC-MS metabolomics generate a fresh insight into assessing the effects of OPFRs on target and non-target aquatic organisms.

Tetracycline Adsorption Performance and Mechanism Using Calcium Hydroxide-Modified Biochars.

Tetracycline is frequently found in various environments and poses significant ecological risks. Calcium hydroxide-modified biochar has shown potential as a material for removing multiple classes of pollutants from wastewater streams. The tetracycline-adsorption performance and mechanism of alkali-modified biochars derived from nine wastes (corn straw, rice straw, swine manure, cypress powder, wheat straw, peanut shell, walnut shell powder, soybean straw, and corncobs) were investigated in the study. Among the four alkalis tested, calcium hydroxide exhibited the most effective modification effects at a pyrolysis temperature of 500 °C. Straw biomass was most suitable to be modified by calcium hydroxide, and calcium hydroxide-modified biochar showed the highest adsorption performance for tetracycline. The maximum adsorption capacities were 8.22 mg g-1 for pristine corn straw biochar and 93.46 mg g-1 for calcium hydroxide-modified corn straw biochar. The tetracycline adsorption mechanism by calcium hydroxide-modified corn straw biochar involved hydrogen bonding, oxygen-containing functional groups, Ca2+ metal complexation, and electrostatic attraction. Consequently, calcium hydroxide-modified corn straw biochar emerges as an environment-friendly, cost-effective, and efficient tetracycline adsorbent.

Organophosphate Pesticides and Pyrethroids in Farmland of the Pearl River Delta, China: Regional Residue, Distributions and Risks.

A regional-scale survey was conducted to assess the occurrence, distribution, and risk of two extensively used pesticides (organophosphate pesticides and pyrethroids) in agricultural soils from the Pearl River Delta (PRD), South China. All target organophosphate pesticides (OPPs) and pyrethroids (PYs) were detected in the soil samples and both with a detection rate of 100%. The residues of the sum of six OPPs and the sum of four PYs were in the range of LOD-991 ng/g and 8.76-2810 ng/g, respectively. Dimethoate was the dominant OPPs, and fenpropathrin was the predominant PYs in the soils of the PRD region. With intensive agricultural activities, higher residues of OPPs and PYs in soils were detected closer to the seaside, among which Zhuhai city and Huizhou city suffered more serious combined pesticide pollution. The vertical compositional profiles showed that dimethoate could be detected through each soil layer in the PRD region's nine cities. The human exposure estimation of OPPs showed insignificant risks to the local population. In contrast, cypermethrin and fenpropathrin showed a potential ecological risk of 2.5% and 3.75% of the sampling sites, respectively. These results can facilitate those commonly used pesticide controls and promote sustainable soil management.

Insight into radical-nonradical coupling activation pathways of peroxymonosulfate by CuxO for antibiotics degradation.

In this work, a heterogeneous catalyst of CuxO was rationally designed by using Cu-based metal organic frameworks (marked Cu-BDC) as the template, and was used to degrade tetracycline (TC) via activation of peroxymonosulfate (PMS). The optimal CuxO-350 showed excellent catalytic efficiency for TC degradation, and the reaction rate constant (0.104 min-1) was 8 times higher than that (0.013 min-1) of raw Cu-BDC. The characterization observations confirmed that CuxO-350 possessed multiple valence states (CuO and Cu2O) and oxygen vacancies (Ov), both of which were favorable for the activation of PMS, resulting in promoting the generation of active species in the CuxO-350 + PMS system. Different from the free radical pathway in Cu-BDC + PMS system, a radical-nonradical coupling process was detected in the CuxO-350 + PMS system, which was confirmed by quenching experiments and EPR measurements. Moreover, the toxicity prediction showed that the toxicity of degradation intermediates declined compared with TC. This work not only opened up a new strategy for the rational design and preparation of high-efficient catalysts by employing metal organic frameworks precursors, but also offered an insight into the reaction mechanism of PMS activation through a radical-nonradical coupling process catalyzed by CuxO-350 derived from Cu-BDC.