Study on the Biomolecular Competitive Mechanism of Polybrominated Diphenyl Ethers and Their Derivatives on Thyroid Hormones.

Polybrominated diphenyl ethers (PBDEs) are widely used brominated flame retardants. PBDEs and their derivatives, hydroxylated PBDEs (OH-PBDEs), can bind to hormone receptors and impact hormone secretion, transportation, and metabolism, leading to endocrine disruption and the development of various diseases. They have particularly strong interference effects on thyroid hormones. This study used decabromodiphenyl ether (BDE-209); 2,2',4,4'-tetrabromodiphenyl ether (BDE-47); and 6-OH-BDE-47 as representative compounds of PBDEs and their derivatives, OH-PBDEs. A fluorescence probe, fluorescein-isothiocyanate-L-thyroxine (FITC-T4, F-T4), specific for binding to transthyretin (TTR), a thyroid transport protein, was prepared. The binding capacity of PBDEs and their derivatives, OH-PBDEs, to TTR was quantitatively measured using fluorescence spectroscopy. The principle of quenching the fluorescence intensity of F-T4 after binding to TTR was used to analyze the competitive interaction between the probe and BDE-209, BDE-47, and 6-OH-BDE-47, thereby evaluating the toxic effects of PBDEs and their derivatives on the thyroid system. Additionally, AutoDock molecular docking software (1.5.6) was used to further analyze the interference mechanism of OH-PBDEs on T4. The results of the study are as follows: (1) Different types of PBDEs and OH-PBDEs exhibit varying degrees of interference with T4. Both the degree of bromination and hydroxylation affect their ability to competitively bind to TTR. Higher bromination and hydroxylation degrees result in stronger competitive substitution. (2) The competitive substitution ability of the same disruptor varies at different concentrations. Higher concentrations lead to stronger substitution ability, but there is a threshold beyond which the substitution ability no longer increases. (3) When OH-PBDEs have four or more bromine atoms and exhibit the most structural similarity to T4, their binding affinity to TTR is stronger than that of T4.

Co-occurrence network in core microorganisms driving the transformation of phosphorous fractionations during phosphorus recovery product used as soil fertilizer.

Phosphorus recovery from water and the subsequent reuse of its products can solve both water eutrophication and phosphorus resource waste issues. However, the potential use of the final recovered products as crop phosphorus fertilizers and the transformation of phosphorus fractions in soils have rarely been analyzed. In this study, the effects of a phosphorus recovery product (w-HC/CSH/P) obtained from our previous phosphorus recovery study on pepper growth were investigated. The association between soil phosphorus fraction transformation and the microbial co-occurrence network was investigated using high-throughput sequencing. The results showed that amendment with w-HC/CSH/P could promote the growth and chlorophyll content of pepper, which exhibited high phosphorus fertilizer efficiency. In addition, applying w-HC/CSH/P in soils could increase the microbial alpha-diversity during pepper cultivation and induce changes in the microbial community, leading to an increase in the relative abundance of Povalibacter, Lysobacter, and GP10 and a decrease in GP17. The proportion of Resin-P and NaHCO3-Po decreased, whereas that of NaOH-Po increased during pepper cultivation. psOTU331 (g_Latescibacteria), psOTU377 (g_Lysobacter), and psOTU461 (g_Pseudoxanthomonas) were the key microorganisms driving the transformation of phosphorus fractionation in the microbial co-occurrence network. Latescibacteria and Lysobacter were closely correlated with the transformation of NaHCO3-Po to NaOH-Po, and Pseudoxanthomonas was significantly correlated with a decrease in Resin-P. These observations highlight the potential of phosphorus recovery products as fertilizer for pepper and provide new insights into the transformation of phosphorus fractions corresponding to the microbiome in soils.

Effect of dissolved humic acids and coated humic acids on tetracycline adsorption by K2CO3-activated magnetic biochar.

Humic acids (HAs) widely exist in water environment, and has an important impact on the adsorption of pollutants. Herein, HAs (both dissolved and coated) was employed to assess the effect on the removal of the organic contaminant tetracycline (TC) by K2CO3 modified magnetic biochar (KMBC). Results showed that low concentration of dissolved HAs promoted TC removal, likely due to a bridging effect, while higher concentration of dissolved HAs inhibited TC adsorption because of the competition of adsorption sites on KMBC. By characterization analysis, coated HAs changed the surface and pore characteristics of KMBC, which suppressed the TC removal. In a sequential adsorption experiment involving dissolved HAs and TC, the addition of HAs at the end of the experiment led to the formation of HAs-TC ligands with free TC, which improved the adsorption capacity of TC. TC adsorption by KMBC in the presence of dissolved HAs and coated HAs showed a downward trend with increasing pH from 5.0 to 10.0. The TC adsorption process was favorable and endothermic, and could be better simulated by pseudo-second-order kinetics and Freundlich isotherm model. Hydrogen bonds and π-π interactions were hypothesized to be the underlying influencing mechanisms.

Potential hazards of biochar: The negative environmental impacts of biochar applications.

Biochar has been widely used as an environmentally friendly material for soil improvement and remediation, water pollution control, greenhouse gas emission reduction, and other purposes because of its characteristics such as a large surface area, porous structure, and abundant surface O-containing functional groups. However, some surface properties (i.e., (i) some surface properties (i.e., organic functional groups and inorganic components), (ii) changes in pH), and (iii) chemical reactions (e.g., aromatic C ring oxidation) that occur between biochar and the application environment may result in the release of harmful components. In this study, biochars with a potential risk to the environment were classified according to their harmful components, surface properties, structure, and particle size, and the potential negative environmental effects of these biochars and the mechanisms inducing these negative effects were reviewed. This article presents a comprehensive overview of the negative environmental impacts of biochar on soil, water, and atmospheric environments. It also summarizes various technical methods of environment-related risk detection and evaluation of biochar application, thereby providing a baseline reference and guiding significance for future biochar selection and toxicity detection, evaluation, and avoidance.

A ratiometric fluorescent probe for visualization of thiophenol and its applications.

Thiophenol has a broad application in agriculture and industry. However, thiophenol can harm to the environment and health for its high toxicity. Developing an effective method for detection of thiophenol in the field of environmental and biology is valuable. In this work, we construct a reaction-based ratiometric fluorescent probe (E)-4-(2-(7-(diethylamino)-2-oxo-2H-chromen-3-yl)vinyl)-1-(4-(2,4-dinitrophenoxy)benzyl)pyridin-1-ium bromide (DCVP-DNP) for probing thiophenol in environment and cells by employing (E)-7-(diethylamino)-3-(2-(pyridin-4-yl)vinyl)-2H-chromen-2-one (DCVP) as the fluorophore and 2,4-dinitrophenyl (DNP) ether as the recognition group for the first time. The probe has high selectivity for thiophenol though thiophenol-triggered nucleophilic substitution reaction. In addition, the ratio of emission intensities of the probe has linearly with thiophenol concentration in the range of 0-65 µM and the detection limit of thiophenol is as low as 4.8 × 10-8 M. Moreover, the probe can not only be applied for detection of thiophenol in water samples, but also image thiophenol in living cells, suggesting its potential application in environment and biological system.

Can microplastics pose a threat to ocean carbon sequestration?

Global climate change has attracted worldwide attention. The ocean is the largest active carbon pool on the planet and plays an important role in global climate change. However, marine plastic pollution is getting increasingly serious due to the large consumption and mismanagement of global plastics. The impact of marine plastics on ecosystem responsible for the gas exchange and circulation of marine CO2 may cause more greenhouse gas emissions. Consequently, in this paper, threats of marine microplastics to ocean carbon sequestration are discussed. Marine microplastics can 1) affect phytoplankton photosynthesis and growth; 2) have toxic effects on zooplankton and affect their development and reproduction; 3) affect marine biological pump; and 4) affect ocean carbon stock. Phytoplankton and zooplankton are the most important producer and consumer of the ocean. As such, clearly, further research should be needed to explore the potential scale and scope of this impact, and its underlying mechanisms.

Functionalized Biochar/Clay Composites for Reducing the Bioavailable Fraction of Arsenic and Cadmium in River Sediment.

Biochar has frequently been used for the treatment of heavy metal pollution in water and soil; its effect on contaminated sediments requires further research. To improve the ability of biochar to immobilize heavy metals in sediment, we prepared a functionalized biochar/attapulgite composite by pyrolysis of the clay attapulgite and zinc chloride-pretreated rice straw biomass. Compared with the original biochar, the biochar/attapulgite composite had a large increase in specific surface area, pore volume, oxygen-containing functional groups, and cation exchange capacity. Biochar effectively improved the dispersibility of attapulgite as a matrix. The results showed that the biochar/attapulgite composite effectively reduced the bioavailable fraction of arsenic (As) and cadmium (Cd) in river sediment, which was a great improvement compared with the raw biochar. After the sediment was treated with different biochar/attapulgite composites, the concentrations of As and Cd in the overlying water and the porewater, and the content of acid-extractable and toxicity characteristic leaching procedure (TCLP)-extractable As and Cd in the solid phase of the sediment decreased significantly. Both zinc chloride activation and attapulgite improved As and Cd immobilization in sediment when we used the biochar/attapulgite composite. The results suggest that biochar/attapulgite composite can be used as an efficient in situ sorbent amendment to improve the heavy metal immobilization ability of the sediment. Environ Toxicol Chem 2019;38:2337-2347. © 2019 SETAC.

Ternary Z-scheme heterojunction of Bi2WO6 with reduced graphene oxide (rGO) and meso-tetra (4-carboxyphenyl) porphyrin (TCPP) for enhanced visible-light photocatalysis.

A highly efficient and new ternary TCPP/rGO/Bi2WO6 Z-scheme heterojunction was designed and fabricated via a facile hydrothermal approach and a liquid ultrasonic route in sequence. The crystal structures, morphologies, microstructures, chemical compositions, elemental states, optical and photo-electrochemical properties of the heterojunction were characterized. This Z-scheme TCPP/rGO/Bi2WO6 photocatalyst has significantly enhanced photocatalytic activity for the tetracycline (TC) degradation under the irradiation of visible light (λ > 420 nm) within 60 min, as compared to pure Bi2WO6, rGO/Bi2WO6 and TCPP/Bi2WO6 composites. The effects of the photocatalyst dosages, pollutant concentrations, coexisting ions and illumination conditions on the photodegradation were investigated. According to the trapping experiments and electron spin resonance analyses, the hole (h+) and superoxide radical (O2-) mainly contribute to the TC decomposition in the TCPP/rGO/Bi2WO6 photocatalytic system. The photodegradation process in the TCPP/rGO/Bi2WO6 ternary composites can be well described by the proposed Z-scheme mechanism. The results indicate that more efficient charge separation, better light absorption, and larger surface area from the developed photocatalyst collectively contribute to the excellent photocatalytic performances. Besides, the photocatalyst has great stability and recyclability with a removal efficiency of 79.27% even after five times of repeated treatment. This work reports a new strategy for the preparation of Z-scheme heterojunction photocatalyst with high photocatalytic activity and provides an alternative for the effective removal of antibiotic wastewater through photocatalysis.

Influence of immobilization on phenanthrene degradation by Bacillus sp. P1 in the presence of Cd(II).

Suspended microbes gradually lost advantages in practical applications of PAHs and heavy metals bioremediation. Therefore this study investigated the effect of immobilization on phenanthrene degradation by Bacillus sp. P1 in the presence of different Cd(II) concentrations. Condensed Bacillus sp. P1 was immobilized with polyvinyl alcohol and sodium alginate and PVA-SA-cell cryogel beads were prepared. The results indicated that the use of gel beads increased the number of adsorption sites thus accelerating phenanthrene degradation. In addition, changes in detoxification indices, including superoxide dismutase (SOD), catalase (CAT) and glutathione (GSH), were determined to elucidate the immobilization mechanisms related to cells protection from Cd(II) when degrading phenanthrene. By protecting the gel membrane, oxidative damage was minimized, while SOD activity increased from 55.72 to 81.33 U/mgprot as Cd(II) increased from 0 to 200 mg/L but later dropped to 44.29 U/mgprot as Cd(II) increased to 300 mg/L for the non-immobilized system. On the other hand, the SOD activity kept increasing from 52.23 to 473.35 U/mgprot for the immobilized system exposed to Cd(II) concentration between 0 and 300 mg/L. For CAT and GSH, immobilization only slowed down the depletion process without any change on the variation trends. The changes in surface properties and physiological responses of microbes caused the differences of immobilization effect on phenanthrene biodegradation in the presence of Cd(II), which is a novel finding.

Influence of sodium dodecyl sulfate coating on adsorption of methylene blue by biochar from aqueous solution.

Biochar is regarded as a promising new class of materials due to its multifunctional character and the possibility of effectively coupling different properties. With increasing introduction into the environment, environmental chemicals such as surfactants will load onto the released biochar and change its physicochemical characteristics and adsorption behavior toward pollutants. In this study, sodium dodecyl sulfate (SDS), as one type of anionic surfactant, was coated onto biochar with different loading amounts. The influence of SDS loading onto biochar's physicochemical properties were investigated by Fourier transform infrared (FT-IR) spectroscopy, elemental analysis, zeta potential and Brunauer-Emmett-Teller (BET) surface area and pore size distribution analysis. Results showed that the pore size of the biochar decreased gradually with the increase of SDS loading because of the surface-adsorption and pore-blocking processes; the pH of the point of zero charge (pHPZC) decreased with increasing SDS loading. Although surface-coating with SDS decreased the pore size of the biochar, its adsorption capacity toward Methylene Blue (MB) significantly increased. The biochar-bound SDS introduced functional groups and negative charges to the biochar surface, which could thus enhance the adsorption of MB via hydrogen bonding and electrostatic interaction. The results can shed light on the underlying mechanism of the influence of anionic surfactants on the adsorption of MB by biochar.

Biochar as potential sustainable precursors for activated carbon production: Multiple applications in environmental protection and energy storage.

There is a growing interest of the scientific community on production of activated carbon using biochar as potential sustainable precursors pyrolyzed from biomass wastes. Physical activation and chemical activation are the main methods applied in the activation process. These methods could have significantly beneficial effects on biochar chemical/physical properties, which make it suitable for multiple applications including water pollution treatment, CO2 capture, and energy storage. The feedstock with different compositions, pyrolysis conditions and activation parameters of biochar have significant influences on the properties of resultant activated carbon. Compared with traditional activated carbon, activated biochar appears to be a new potential cost-effective and environmentally-friendly carbon materials with great application prospect in many fields. This review not only summarizes information from the current analysis of activated biochar and their multiple applications for further optimization and understanding, but also offers new directions for development of activated biochar.

Bioremediation mechanisms of combined pollution of PAHs and heavy metals by bacteria and fungi: A mini review.

In recent years, knowledge in regard to bioremediation of combined pollution of polycyclic aromatic hydrocarbons (PAHs) and heavy metals by bacteria and fungi has been widely developed. This paper reviews the species of bacteria and fungi which can tackle with various types of PAHs and heavy metals entering into environment simultaneously or successively. Microbial activity, pollutants bioavailability and environmental factors (e.g. pH, temperature, low molecular weight organic acids and humic acids) can all affect the bioremediation of PAHs and heavy metals. Moreover, this paper summarizes the remediation mechanisms of PAHs and heavy metals by microbes via elucidating the interaction mechanisms of heavy metals with heavy metals, PAHs/PAHs metabolites with PAHs and PAHs with heavy metals. Based on the above reviews, this paper also discusses the potential research needs for this field.

Effect of rhamnolipid solubilization on hexadecane bioavailability: enhancement or reduction?

In this study, liquid culture systems containing rhamnolipid-solubilized, separate-phase, and multi-state hexadecane as the carbon source were employed for examining the effect of rhamnolipid solubilization on the bioavailability of hexadecane. Experimental results showed that the uptake of rhamnolipid-solubilized hexadecane by Pseudomonas aeruginosa ATCC 9027, a rhamnolipid producing strain, was enhanced compared to the uptake of mass hexadecane as a separate phase, indicating rhamnolipid solubilization increased the bioavailability of hexadecane for this bacterium. For Pseudomonas putida CICC 20575 which does not produce but degrade rhamnolipid, the uptake of either rhamnolipid-solubilized hexadecane or multi-state hexadecane was inhibited. The reduction of bioavailability was assumed to be the consequence of the blocking effect caused by the partition of rhamnolipid molecules at the hexadecane-water interface. The results show that how rhamnolipid solubilization changes the bioavailability of hexadecane depends on the bacterial compatibility to rhamnolipid. The study adds insight into the knowledge of biosurfactant-associated bioavailability of hydrophobic organic compounds (HOCs), and is of importance for application of biosurfactants in bioremediation of HOCs.

Investigation of the adsorption-reduction mechanisms of hexavalent chromium by ramie biochars of different pyrolytic temperatures.

To investigate the relationship between Cr(VI) adsorption mechanisms and physio-chemical properties of biochar, ramie residues were oxygen-limited pyrolyzed under temperature varying from 300 to 600°C. Batch adsorption experiments indicated that higher pyrolysis temperature limits Cr(VI) sorption in terms of capacity and affinity due to a higher aromatic structure and fewer polar functional groups in biochar. Both electrostatic (physical) and ionic (chemical) interactions were involved in the Cr(VI) removal. For low-temperature biochar, the simple physical adsorption was limited and the significant improvement in Cr(VI) sorption was attributed to abundant carboxyl and hydroxyl groups. The adsorption-reduction mechanisms could be concluded that Cr(VI) ions were electrostatically attracted by the positively charged biochar surface and reduced to Cr(III), and then the converted Cr(III) was retained or discharged into the solution. The study demonstrates ramie residues can be converted into biochar as a low-cost and effective sorbent for Cr(VI) removal.

Effect of aniline on cadmium adsorption by sulfanilic acid-grafted magnetic graphene oxide sheets.

Cd(II) has posed severe health risks worldwide. To remove this contaminant from aqueous solution, the sulfanilic acid-grafted magnetic graphene oxide sheets (MGOs/SA) were prepared and characterized. The mutual effects of Cd(II) and aniline adsorption on MGOs/SA were studied. The effects of operating parameters such as pH, ionic strength, contact time and temperature on the Cd(II) enrichment, as well as the adsorption kinetics and isotherm were also investigated. The results demonstrated that MGOs/SA could effectively remove Cd(II) and aniline from the aqueous solution and the two adsorption processes were strongly dependent on solution pH. The Cd(II) adsorption was reduced by the presence of aniline at pH<5.4 but was improved at pH>5.4. The presence of Cd(II) diminished the adsorption capacity for aniline at pH<7.8 but enhanced the aniline adsorption at pH>7.8. The decontamination of Cd(II) by MGOs/SA was influenced by ionic strength. Besides, the adsorption process could be well described by pseudo-second-order kinetic model. The intraparticle diffusion study revealed that the intraparticle diffusion was not the only rate-limiting step for the adsorption process. Moreover, the experimental data of isotherm followed the Freundlich isotherm model.