Natural mineral colloids facilitated transport of EE2 in saturated porous media: Effects of humic acid and conjugate form.

Steroid estrogens have posed significant ecological risks to aquatic organisms due to their potent endocrine-disrupting effects. The role of natural mineral colloids in facilitating the transport of hydrophobic organic pollutants in the environment has been confirmed, but the control mechanisms of colloids on 17α-Ethinylestradiol (EE2) migration in the subsurface environment are often still not well understood. This study combined the batch sorption equilibrium experiments and dynamic transport simulations to reveal the interface interactions and co-transport characteristics between illite colloids and EE2 at both macroscopic and microscopic levels. The existing form changes of EE2 and the influence of coexisting humic acid (HA) during transport in porous media were also specifically investigated. The batch experiments demonstrated that the primary mechanisms governing EE2 sorption onto illite colloids involved surface sorption and hydrogen bonding. The coexistence of HA could load onto the surface of illite colloids, thereby enhancing the colloidal sorption capacity for EE2. Transport experiments demonstrated that the migratory ability of EE2 in silty clay was limited, but illite colloids could significantly promote its penetration, with the peak penetration content (Ct/C0) increasing from 0.64 to 0.77. In the absence of HA, EE2 primarily transported in a dissolved form, accounting for 62.86% of the total concentrations. When HA concentrations were increased to 10 mg/L and 20 mg/L, the proportion of colloidal conjugate EE2 in the effluents reached 52.13% and 54.49%, respectively. The enhanced transport of EE2 by HA was primarily attributed to the improved migration ability of illite colloids and the increased proportion of illite-EE2 conjugate, resulting in a maximum Ct/C0 value of 0.94. The validity of these results was further confirmed by employing calculations based on the Derjaguin-Landau-Verwey-Overbeek and Colloidal Filtration Theory. This study provides new insights of understanding the transport of EE2 in subsurface environment.

Application of cold-adapted microbial agents in soil contaminate remediation: biodegradation mechanisms, case studies, and safety assessments.

The microbial agent technology has made significant progress in remediating nitro-aromatic compounds (NACs), such as p-nitrophenol, 2,4-dinitrophenol, and 2,4,6-Trinitrotoluene, in farmland soil over the past decade. However, there are still gaps in our understanding of the bioavailability and degradation mechanisms of these compounds in low-temperature environments. In this review, we provide a comprehensive summary of the strategies employed by cold-adapted microorganisms and elucidate the degradation pathways of NACs pollutants. To further analyze their metabolic mechanisms, we propose using mass balance to improve our understanding of biochemical processes and refine the degradation pathways through stoichiometry analysis. Additionally, we suggest employing 13C-metabolic flux analysis to track enzyme activity and intermediate products during bio-degradation processes with the aim of accelerating the remediation of nitro-aromatic compounds, particularly in cold regions. Through a comprehensive analysis of pollutant metabolic activities and a commitment to the 'One Health' approach, with an emphasis on selecting non-pathogenic strains, the environmental management strategies for soil remediation could be positioned to develop and implement safe and effective measure.

Effects of freeze-thaw cycles on soil greenhouse gas emissions: A systematic review.

In the context of global warming, increasingly widespread and frequent freezing and thawing cycles (FTCs) will have profound effects on the biogeochemical cycling of soil carbon and nitrogen. FTCs can increase soil greenhouse gas (GHG) emissions by reducing the stability of soil aggregates, promoting the release of dissolved organic carbon, decreasing the number of microorganisms, inducing cell rupture, and releasing carbon and nitrogen nutrients for use by surviving microorganisms. However, the similarity and disparity of the mechanisms potentially contributing to changes in GHGs have not been systematically evaluated. The present study consolidates the most recent findings on the dynamics of soil carbon and nitrogen, as well as GHGs, in relation to FTCs. Additionally, it analyzes the impact of FTCs on soil GHGs in a systematic manner. In this study, particular emphasis is given to the following: (i) the reaction mechanism involved; (ii) variations in soil composition in different types of land (e.g., forest, peatland, farmland, and grassland); (iii) changes in soil structure in response to cycles of freezing temperatures; (iv) alterations in microbial biomass and community structure that may provide further insight into the fluctuations in GHGs after FTCs. The challenges identified included the extension of laboratory-scale research to ecosystem scales, the performance of in-depth investigation of the coupled effects of carbon, nitrogen, and water in the freeze-thaw process, and analysis of the effects of FTCs through the use of integrated research tools. The results of this study can provide a valuable point of reference for future experimental designs and scientific investigations and can also assist in the analysis of the attributes of GHG emissions from soil and the ecological consequences of the factors that influence these emissions in the context of global permafrost warming.

Fe-MnO2 nanosheets loading dihydroartemisinin for ferroptosis and immunotherapy.

Ferroptosis has emerged as a therapeutic tactic to trigger cancer cell death driven by abnormal accumulation of reactive oxygen species (ROS). However, a single ferroptosis treatment modality is often limited. In this work, a combination therapy of ferroptosis and immunotherapy for cancer was proposed. Specifically, a versatile nanodrug was designed for the multiple treatment of hepatocellular carcinoma (HCC) by loading dihydroartemisinin (DHA) on Fe3+-doped MnO2 nanosheets (Fe-MnO2/DHA). Firstly, Fe-MnO2/DHA was degraded by glutathione (GSH) in the tumor microenvironment (TME) to release Fe2+, Mn2+ and DHA, leading to aberrant ROS accumulation due to Fenton/Fenton-like reaction. Secondly, breakage of endoperoxide bridge from DHA was caused by Fe2+ to further induce oxidative stress. Thirdly, the depleted GSH promoted the inactivation of glutathione peroxidase 4 (GPX4), resulting in lipid peroxide (LPO) accumulation. The resulting LPO and ROS could induce ferroptosis and apoptosis of liver cancer cells. Furthermore, Fe-MnO2/DHA mediated three-pronged stimulation of oxidative stress, resulting in high levels of targeted immunogenic cell death (ICD). It could enhance the infiltration of CD4+ T and CD8+ T cells, and promote macrophage polarization. DHA also acted as an immunomodulator to inhibit regulatory T cells (Tregs) for systemic antitumor. Overall, Fe-MnO2/DHA presents a multi-modal therapy for HCC driven by ferroptosis, apoptosis and immune activation, significantly advancing synergistic cancer treatment.

The response of steroid estrogens bioavailability to various sorption mechanisms by soil organic matter extracted with sequential alkaline-extraction method from an agriculture soil.

The long-term groundwater contamination risks posed by steroidal estrogens (SEs) in animal-manured agricultural soils are closely associated with the soil organic matter (SOM) content and composition. In this study, the bioavailability of estrone (E1) and 17ß-estradiol (17ß-E2) under different sorption mechanism in humic acids (HA1 and HA2) and humin (HM) extracted with sequential alkaline-extraction technique (SAET) were examined. These SOMs extracted by SAET showed various properties and sorption characteristics for SEs. The alkyl carbon and condensed SOM increased during SAET, but aromatic carbon decreased and the same trend for polarity. Quick sorption was the major SEs sorption mechanism on HA1 and HA2, which contributed more than 69%; whilst slow sorption rate was about 50% in soil and HM. The logKoc values were proportional to the TOC of SOM according to Freundlich fitting, and the sorption capacity of sorbent for E1 and 17ß-E2 was related to the logKow values, indicating that the main mechanism controlling the SEs sorption was hydrophobic interaction. The larger micropore volume of HM and soil was more conducive to the micropore filling of SEs. Meanwhile, the specific sorption of SEs on condensed domain of SOM was the main reason for the strong desorption hysteresis and slow sorption in HM and soil. The SEs degradation rate was positively correlated with the contribution rate of quick adsorption and negatively correlated with the contribution rate of slow adsorption, indicating that the bioavailability of SEs sorbed by hydrophobic interaction was higher than that of micropore filling or specific sorption, which was also the reason for the low bioavailability of SEs in HM and soil. This work confirms the regulation of on-site SOM compositions and their properties on SEs sorption and bioavailability. Characterization of these details is crucial for the improved prediction of long-term risks to groundwater.

Isolation of functional bacterial strains from chromium-contaminated site and bioremediation potentials.

In this study, two Cr(VI)-reducing functional bacterial strains (TJ-1 and TJ-5) were successfully isolated and screened from the chromium-contaminated soil from a real site. The 16S rRNA gene sequences were analysed, which showed high similarity (>99%) with Stenotrophomonas maltophilia (TJ-1) and Brucella intermedius (TJ-5) species. The optimum growth for the two bacteria to reduce Cr(VI) were achieved at pH 7.0 and initial inoculation amount of 5%. The two strains were applied to real contaminated soil samples and showed better Cr removal when external carbon sources were added. Using sawdust as a solid-phase carbon source supplement, both TJ-1 and TJ-5 showed higher remediation efficiency (99.77% and 93.86%) than using glucose as the carbon source (68.56% and 70.87%). Results of the stability of soil Cr(VI) bioremediation revealed that the water-soluble Cr(VI) content of bioremediated sample remained unchanged, indicating that Cr(VI) is not easily released after death of the strains. Solid-phase carbon source supplements may help the cells to attach and grow into biofilms, creating a better growth condition which improved the remediation efficiency. Column experiments showed that the total remediation efficiencies by the two strains were 34.23% and 20.63%, respectively, within a short time period (76 h). Therefore, the two strains showed great bioremediation potentials for chromium-contaminated sites and can be used in future application of in-situ bioremediation.

Sustainable Chromium (VI) Removal from Contaminated Groundwater Using Nano-Magnetite-Modified Biochar via Rapid Microwave Synthesis.

This study developed a nano-magnetite-modified biochar material (m-biochar) using a simple and rapid in situ synthesis method via microwave treatment, and systematically investigated the removal capability and mechanism of chromium (VI) by this m-biochar from contaminated groundwater. The m-biochar was fabricated from reed residues and magnetically modified by nano-Fe3O4. The results from scanning electron microscopy (SEM) and X-ray diffraction (XRD) characterisations confirmed the successful doping of nano-Fe3O4 on the biochar with an improved porous structure. The synthesised m-biochar exhibited significantly higher maximum adsorption capacity of 9.92 mg/g compared with that (8.03 mg/g) of the pristine biochar. The adsorption kinetics followed the pseudo-second-order model and the intraparticle diffusion model, which indicated that the overall adsorption rate of Cr(VI) was governed by the processes of chemical adsorption, liquid film diffusion and intramolecular diffusion. The increasing of the pH from 3 to 11 significantly affected the Cr(VI) adsorption, where the capabilities decreased from 9.92 mg/g to 0.435 mg/g and 8.03 mg/g to 0.095 mg/g for the m-biochar and pristine biochar, respectively. Moreover, the adsorption mechanisms of Cr(VI) by m-biochar were evaluated and confirmed to include the pathways of electrostatic adsorption, reduction and complexation. This study highlighted an effective synthesis method to prepare a superior Cr(VI) adsorbent, which could contribute to the effective remediation of heavy metal contaminations in the groundwater.

Biodegradation of Phenol by Rhodococcus sp. Strain SKC: Characterization and Kinetics Study.

This study focuses on the kinetics of a pure strain of bacterium Rhodococcus sp. SKC, isolated from phenol-contaminated soil, for the biodegradation of phenol as its sole carbon and energy source in aqueous medium. The kinetics of phenol biodegradation including the lag phase, the maximum phenol degradation rate, maximum growth rate (Rm) and maximum yield coefficient (Y) for each Si (initial phenol concentration, mg/L) were fitted using the Gompertz and Haldane models of substrate inhibition (R2 > 0.9904, RMSE < 0.00925). The values of these parameters at optimum conditions were µmax = 0.30 h-1, Ks = 36.40 mg/L, and Ki = 418.79 mg/L, and that means the inhibition concentration of phenol was 418.79 mg/L. By comparing with other strains of bacteria, Rhodococcus sp. SKC exhibited a high yield factor and tolerance towards phenol. This study demonstrates the potential application of Rhodococcus sp. SKC for the bioremediation of phenol contaminate.

The sources and dispersal of nitrate in multiple waters, constrained by multiple isotopes, in the Wudalianchi region, northeast China.

The Wudalianchi scenic area in NE China has been named an UNESCO "Global Geopark" and "Biosphere Reserve." During this investigation, the sources of nitrate and the hydrologic system through which it is dispersed were assessed using geochemical data and a multiple isotopic approach. The cold waters from the south and north springs originated from the deep subsurface. Isotopically, these waters exhibited relatively negative δD and δ18O values and nitrate in the water was substantially depleted 15N, suggesting that the mineral water was primarily derived from depth. Lakes within the Wudalianchi region were primarily composed of water from these deep mineral springs and precipitation. Chemical fertilizers were the primary source of nitrate to the Wudalianchi lakes. Groundwater was found in shallow mineral springs and wells plotted above the local meteoric water line, implying that shallow groundwater was primarily derived from precipitation. Elevated concentrations of nitrate in shallow mineral springs and well waters during the summer, autumn, and winter suggest that shallow groundwater within the Yaoquan volcanic area was also polluted by nitrate from human activities. Denitrification of shallow groundwater is slow, reducing the potential for "self-remediation". The concentration data are supported by nitrogen (N) isotope data; wells and springs exhibited N isotopic ratios between - 5‰ and + 5‰ (typical of fertilizers and precipitation) and exhibited higher oxygen (O) isotope values than water in the Wudalianchi lakes. These relationships suggest that nitrate in shallow mineral springs, wells, and lakes near the Yaoquan volcano was derived from the mixing of chemical fertilizers with local summer rainfall.

Adsorption performance and mechanism of magnetic reduced graphene oxide in glyphosate contaminated water.

In this study, the magnetic reduced graphene oxide (RGO/Fe3O4), with easy separation and high adsorption performance, was prepared and used to treat glyphosate (GLY) contaminated water. GLY adsorption performance of RGO/Fe3O4 was investigated, and influences of pH, adsorption time, temperature, contaminant concentration, and competing anions were analyzed. Moreover, the adsorption mechanism was discussed in the light of several characterization methods, including scanning electron microscopy (SEM), energy dispersive spectrum (EDS), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the RGO/Fe3O4 presented a significant GLY adsorption capacity and acid condition was beneficial for this adsorption. The pseudo-second-order kinetic model and the Langmuir model correlated satisfactorily to the experimental data, indicating that this process was controlled by chemical adsorption and monolayer adsorption. Thermodynamic studies revealed that the adsorption of glyphosate onto RGO/Fe3O4 was spontaneous, endothermic, and feasible process. High temperatures were beneficial to GLY adsorption. The GLY adsorption mechanism of RGO/Fe3O4 was mainly attributed to hydrogen-bond interaction, electrostatic interaction, and coordination. Therefore, the RGO/Fe3O4 investigated in this research may offer an attractive adsorbent candidate for treatment of glyphosate contaminated water and warrant further study as a mechanism for glyphosate efficient removal.

Environmental risk assessment of the emerging EDCs contaminants from rural soil and aqueous sources: Analytical and modelling approaches.

The emerging endocrine disrupting chemicals posed high risk and much uncertainty to eco-environment and human health. An analytical method, developed for the simultaneous determination of five steroid estrogens in groundwater and soil based upon solid phase extraction and gas chromatography-mass spectrometry, was applied to investigate the distribution of estrone and 17ß-estradiol around Shenyang City with particular focus on penetrating from surface to groundwater in this study. Mean concentrations of the estrone and 17ß-estradiol were 55.1 ng L-1 and 56.1 ng L-1 in groundwater, 32.5 ng g-1 and 23.1 ng g-1 in soil, respectively. The distribution of estrone and 17ß-estradiol were similar in groundwater, the concentration in the west of the site center was relatively low, and the surroundings were relatively high. The concentration of estrone was changed less, but 17ß-estradiol was significantly increased in silt and silty sand layers in vadose zone profiles. Both estrone and 17ß-estradiol concentrations changed abruptly at the interface of layers. Incorporating the temporal and spatial evolution of physical-chemical-biological environmental parameters at the sites, sorption and biodegradation were suggested the controlling roles in the fate and transport of SEs in the soil-groundwater system. The Ecological risk quotients values of both soil and groundwater indicated a very high ecological risk associated with SEs, but the non-carcinogenic harm quotients did not exceed the acceptable level of non-carcinogenic human health risk.

Low-temperature biodegradation of aniline by freely suspended and magnetic modified Pseudomonas migulae AN-1.

Aniline is of great environmental concern with regards to widespread occurrence in water and soil and increasing threat into the life forms. Bioremediation involving the use of degrading bacterium in the removal of aniline is the most promising process, yet inhibited under low temperature usually. In the present study, a new psychrotrophic bacterial strain isolated from groundwater, designated AN-1, was shown to be capable of aniline degradation in a concentration range of 135-2202 mg L(-1) within 72 h at 10 °C. Strain AN-1 was proposed to be a Pseudomonas migulae group of bacteria based on the evolutionary relationship and the morphological and biochemical characteristics. The pH, NaH2PO4, and aniline concentration were used as independent variables to optimize the aniline removal by AN-1 at 10 °C, and a statistically significant (R (2) = 0.9230, p < 0.005) quadratic polynomial mathematical model was suggested. Moreover, an efficient biocomposite by assembling Fe3O4 nanoparticles onto the surface of AN-1 cells was constructed. Compared with free cells, the microbial cell/Fe3O4 biocomposite had the same biodegradation activity but exhibited remarkable reusability. This study highlights AN-1 might be a promising candidate for aniline removal from wastewater at low temperatures.