Predicting the binding configuration and release potential of heavy metals on iron (oxyhydr)oxides: A machine learning study on EXAFS.

Heavy metals raise a global concern and can be easily retained by ubiquitous iron (oxyhydr)oxides in natural and engineered systems. The complex interaction between iron (oxyhydr)oxides and heavy metals results in various mineral-metal binding configurations, such as outer-sphere complexes and edge-sharing inner-sphere complexes, which determine the accumulation and release of heavy metals in the environment. However, traditional experimental approaches are time-consuming and inadequate to elucidate the complex binding relationships and configurations between iron (oxyhydr)oxides and heavy metals. Herein, a workflow that integrates the binding configuration data of 11 heavy metals on 7 iron (oxyhydr)oxides and then trains machine learning models to predict unknown binding configurations was proposed. The well-trained multi-grained cascade forest models exhibited high accuracy (> 90%) and predictive performance (R2 ∼ 0.75). The underlying effects of mineral properties, metal ion species, and environmental conditions on mineral-metal binding configurations were fully interpreted with data mining. Moreover, the metal release rate was further successfully predicted based on mineral-metal binding configurations. This work provides a method to accurately and quickly predict the binding configuration of heavy metals on iron (oxyhydr)oxides, which would provide guidance for estimating the potential release behavior of heavy metals and remediating heavy metal pollution in natural and engineered environments.

F-box and leucine-rich repeat protein 16 controls tamoxifen sensitivity via regulation of mitochondrial respiration in estrogen receptor-positive breast cancer cells.

Tamoxifen is one of the most effective therapeutic tools for estrogen receptor-positive (ER +) breast cancer. However, the intrinsic insensitivity and resistance to tamoxifen remains a significant hurdle for achieving optimal responses and curative therapy. In this study, we report that F-box and leucine-rich repeat protein 16 (FBXL16) is located in the mitochondria of ER + breast cancer cells. The mitochondrial FBXL16 plays an essential role in sustaining mitochondrial respiration and thereby regulates the sensitivity of ER + breast cancer cells to tamoxifen treatment. Importantly, high FBXL16 expression is significantly correlated with poor overall survival of ER + breast cancer patients. Moreover, mitochondrial inhibition phenocopies FBXL16 depletion in terms of sensitizing the ER + breast cancer cells to tamoxifen treatment. Together, our study demonstrates that FBXL16 acts as a novel regulator of tamoxifen sensitivity. Thus, targeting FBXL16 may serve as a promising approach for improving the therapeutic efficacy of tamoxifen in ER + breast cancer cells.

Adsorption of lead and antimony in the presence and absence of EDTA by a new vermiculite product with potential recyclability.

A new two-step modification method has been proposed where 1.8% HCl and 3.1% HNO3 were applied to modify the interlayer of vermiculite (VMT). This product was given 90 °C of heat in 30% H2SO4 solution that was used for Pb (II) and Sb (III) adsorption. The EDTA presence on the individual adsorption was assessed. X-ray diffraction revealed that the VMT inter-stratified reflection through acid intercalation within the interlayer decreased the parallel gaps between the atoms, witnessing on the outer-sphere adsorption. The driving force was found electrostatic, which fits well with pseudo-second-order kinetics and Langmuir isotherm. The Pb (II) and Sb (III) uptake followed descending order adsorption with increasing concentration of chelating EDTA. Three consecutive desorption cycles revealed that the prepared adsorbent was suitable that may be regarded as a good candidate for complex wastewaters.

A novel ball-milled aluminum-carbon composite for enhanced adsorption and degradation of hexabromocyclododecane.

Hexabromocyclododecane (HBCD) is one of the priority persistent organic pollutants (POPs), yet a cost-effective technology has been lacking for the removal and degradation of HBCD. Zero-valent aluminum (ZVAl) is an excellent electron donor. However, the inert and hydrophilic surface oxide layer impedes the release of the electrons from the core metallic Al, resulting in poor reactivity towards HBCD. In this research, a new type of modified mZVAl particles (AC@mZVAlbm/NaCl) were prepared through ball milling mZVAl in the presence of activated carbon (AC) and NaCl, and tested for adsorption and reductive degradation of HBCD in water. AC@mZVAlbm/NaCl was characterized with a metallic Al core with newly created reactive surface coated with a thin layer of crushed carbon nanoparticles. AC@mZVAlbm/NaCl was able to rapidly (within 1 h) adsorb HBCD (C0 = 2 mg L-1) and thus effectively enriched HBCD on the carbon surface of AC@mZVAlbm/NaCl. The pre-enriched HBCD was subsequently degraded by the electrons from the core Al, and ∼63.44% of the pre-sorbed HBCD was completely debrominated after 62 h of the contact. A notable time lag (∼12 h) from the onset of the adsorption to the debromination was observed, signifying the importance of the solid-phase mass transfer from the initially adsorbed AC particles to the reactive Al-AC interface. Overall, AC@mZVAlbm/NaCl synergizes the adsorptive properties of AC and the high reactivity of metallic Al, and enables a novel two-step adsorption and reductive degradation process for treating HBCD or likely other POPs.

Degradation of hexabromocyclododecane (HBCD) by nanoscale zero-valent aluminum (nZVAl).

Hexabromocyclododecane (HBCD) has been listed in Annex A of the Stockholm Convention on Persistent Organic Pollutants (POPs) in 2013, but till now there is a lack of efficient methods for its degradation. In this study, nanoscale zero-valent aluminum (nZVAl), an excellent reductant with a very low redox potential of E0(Al3+/Al0) = -1.662 V and strong electron transfer ability, was used to reductively degrade HBCD. Nearly 100% HBCD was degraded within 8 h reaction at 25 °C in ethanol/water (v/v, 50/50) solution without pH adjustment. And about 67% cyclododecatriene (CDT) was obtained, which is the complete debromination product. What's more, the yield of Br- could achieve nearly 100% after optimizing conditions. The reaction was strongly promoted by increasing the dosages of nZVAl or decreasing the initial concentration of HBCD. The temperature had the most significant influence and the degradation was completed in 40 min with elevating the reaction temperature to 45 °C. The reaction mechanism was further revealed through the characterization of nZVAl particles before and after the reaction by SEM-EDS, TEM, HRTEM, XRD, and XPS. It was found that, after corrosion of the oxide film on the surface of nZVAl, metallic aluminum inside was exposed. The reactive sites were provided and electrons released were transferred from nZVAl to HBCD, causing HBCD degraded to dibromocyclododecadiene (DBCD) and then CDT by reductive debromination. These findings imply that nZVAl can degrade HBCD efficiently with no extra energy input and this offers a new idea for better treatment of HBCD.

Environmental application of MgMn-layered double oxide for simultaneous efficient removal of tetracycline and Cd pollution: Performance and mechanism.

The MgMn-layered double oxide (MgMn-LDO), which was fabricated by calcining MgMn-layered double hydroxide (MgMn-LDH), was used to remove tetracycline (TC) and cadmium (Cd) pollution. In MgMn-LDO activated peroxymonosulfate (PMS) system, 97.1% of TC was degraded within 20 min. The high oxidizing sites exposed on MgMn-LDO surface played a main role on activating PMS to generate OH, SO4-, O2- and 1O2 (the key species) for TC degradation. MgMn-LDO could keep excellent degradation performance in a wide range of pH (from 4 to 10). The degradation degree of TC in distilled water is basically the same as that in Pearl River water, and even above 80% of TC could be degraded in human urine. The good reusability and high structure stability of MgMn-LDO were further verified. Meanwhile, Cd immobilization on MgMn-LDO reached equilibrium within 10 min, and its maximum fixed quantity was 8.234 mmol g-1 (922.208 mg g-1). The outstanding Cd fixed ability resulted from the formation of CdCO3 and Cd (OH)2. In combined system, the existence of TC promoted the immobilization of Cd on MgMn-LDO. Low concentration of Cd (0.0125 mM) had synergism effect on TC degradation, while high concentration of Cd (0.025 and 0.05 mM) had inhibiting action. Finally, a column filled with MgMn-LDO was designed for repairing TC and Cd pollution hierarchically. This study provided an effective strategy to clean up the organic-heavy metal combined pollution.

Synergistic deep removal of As(III) and Cd(II) by a calcined multifunctional MgZnFe-CO3 layered double hydroxide: Photooxidation, precipitation and adsorption.

A high removal rate (>99.7%) of combined arsenite (As(III)) and Cd (Cd(II)) in low concentration (1000 µg/L) from contaminated water was achieved by a calcined MgZnFe-CO3 layered double hydroxide (CMZF) adsorbent. Batch control studies and a series of spectroscopy detection technologies were employed to investigate the removal mechanism and interactions between As(III) and Cd(II) on the interface of water/CMZF. Synergistic adsorption and photooxidation occurred based on the systematical kinetic and isotherm studies. The enhanced removal of As(III) was achieved by the photooxidation, formation of ternary As(III)Cd(II) surface complexes and enhanced hydrogen bond. Meanwhile, oxidative formed negative charged As(V) could reduce the electrostatic repulsion force between Cd(II) cations and play a role as anion bridging, consequently resulted in a stronger attraction between CMZF and Cd(II). Combined with the verdicts of relevant characterizations such as XRD, XPS and EPR, it was assumed that the deep co-removal mechanism could be attributed to the coupling of various processes including intercalation, complexation, photooxidation of As(III) and precipitation of CdCO3. Moreover, the successful removal of As(III) and Cd(II) from real water matrix qualified the CMZF a potentially attractive adsorbent for both As(III) and Cd(II) deep treatment in practical engineering.

[IgG antibody level in saliva from rabbits infected with Trichinella spiralis].

Twenty-eight Japanese big ear rabbits were randomly divided into control group and experimental group. Twenty rabbits in experimental group were each infected with 3000 larvae of Trichinella spiralis. Serum and saliva samples were collected at pre-infection and every week after infection, and were examined for IgG antibody by indirect ELISA using T. spiralis muscle larvae excretory-secretory antigen (MLESA). At 1, 2, 3, 4, 5 and 6 weeks afer infection, the positive rate in saliva samples was 10%, 15%, 40%, 65%, 85%, and 95%, respectively; and that of serum samples was 35%, 50%, 80%, 90%, 100%, and 100%, respectively. The positive rate was significantly different between saliva and serum samples at 1, 2 and 3 weeks post-infection (chi2 = 3.58, 5.23, 6.67, P < 0.05), but no significant difference at 4, 5, and 6 weeks post-infection (chi = 0.12, 1.03, 1.03, P > 0.05). The results indicate that the indirect ELISA using MLESA to detect IgG antibody in saliva may be helpful for clinical diagnosis of trichinellosis.