Feasibility and solidification mechanism study of self-sustaining smoldering remediation for copper and lead-contaminated soil.

Soil heavy metal pollution is an important issue that affects human health and ecological well-being. In-situ thermal treatment techniques, such as self-sustaining smoldering combustion (SSS), have been widely studied for the treatment of organic pollutants. However, the lack of fuel in heavy metal-contaminated soil has hindered its application. In this study, we used corn straw as fuel to investigate the feasibility of SSS remediation for copper and lead in heavy metal-contaminated soil, as well as to explore the remediation mechanism. The results of the study showed that SSS increased soil pH, electrical conductivity (EC), total phosphorus (TP), total potassium (TK), rapidly available phosphorus (AP), and available potassium (AK), while decreasing total nitrogen (TN), alkali-hydrolyzed nitrogen (AN), and cation exchange capacity (CEC). The oxidation state of copper (Cu) increased from 10% to 21%-40%, and the residual state of lead (Pb) increased from 18% to 51%-73%. The Toxicity characteristic leaching procedure (TCLP) of Cu decreased by a maximum of 81.08%, and the extracted state of Diethylenetriaminepentaacetic acid (DTPA) decreased by 67.63%; the TCLP of Pb decreased by a maximum of 81.87%, and DTPA decreased by a maximum of 85.68%. The study indicates that SSS using corn straw as fuel successfully achieved remediation of heavy metal-contaminated soil. However, SSS does not reduce the content of copper and lead; it only changes their forms in the soil. The main reasons for the fixation of copper and lead during the SSS process are the adsorption of biochar, complexation with -OH functional groups, binding with π electrons, and the formation of crystalline compounds. This research provides a reference for the application of SSS in heavy metal-contaminated soil and has potential practical implications.

Interactions between inhalable aged microplastics and lung surfactant: Potential pulmonary health risks.

The relationship between microplastics (MPs) and human respiratory health has garnered significant attention since inhalation constitutes the primary pathway for atmospheric MP exposure. While recent studies have revealed respiratory risks associated with MPs, virgin MPs used as plastic surrogates in these experiments did not represent the MPs that occur naturally and that undergo aging effects. Thus, the effects of aged MPs on respiratory health remain unknown. We herein analyzed the interaction between inhalable aged MPs with lung surfactant (LS) extracted from porcine lungs vis-à-vis interfacial chemistry employing in-vitro experiments, and explored oxidative damage induced by aged MPs in simulated lung fluid (SLF) and the underlying mechanisms of action. Our results showed that aged MPs significantly increased the surface tension of the LS, accompanied by a diminution in its foaming ability. The stronger adsorptive capacity of the aged MPs toward the phospholipids of LS appeared to produce increased surface tension, while the change in foaming ability might have resulted from a variation in the protein secondary structure and the adsorption of proteins onto MPs. The adsorption of phospholipid and protein components then led to the aggregation of MPs in SLF, where the aged MPs exhibited smaller hydrodynamic diameters in comparison with the unaged MPs, likely interacting with biomolecules in bodily fluids to exacerbate health hazards. Persistent free radicals were also formed on aged MPs, inducing the formation of reactive oxygen species such as superoxide radicals (O2•-), hydrogen peroxide (HOOH), and hydroxyl radicals (•OH); this would lead to LS lipid peroxidation and protein damage and increase the risk of respiratory disease. Our investigation was the first-ever to reveal a potential toxic effect of aged MPs and their actions on the human respiratory system, of great significance in understanding the risk of inhaled MPs on lung health.

Red mud with enhanced dealkalization performance by supercritical water technology for efficient SO2 capture.

The total de-alkalization treatment of industrial solid waste red mud (RM) has been a worldwide challenge. Removing the insoluble structural alkali fraction from RM is the key to enhancing the sustainable utilization of RM resources. In this paper, supercritical water (SCW) and leaching agents were used for the first time to de-alkalize the Bayer RM and to remove sulfur dioxide (SO2) from flue gas with the de-alkalized RM slurry. The results showed that the optimum alkali removal and Fe leaching rates of RM-CaO-SW slurry were 97.90 ± 0.88% and 82.70 ± 0.95%, respectively. Results confirmed that the SCW technique accelerated the disruption of (Al-O) and (Si-O) bonds and the structural disintegration of aluminosilicate minerals, facilitating the conversion of insoluble structural alkalis to soluble chemical alkalis. The exchangeable Ca2+ displaced Na+ in the remaining insoluble base, producing soluble sodium salts or alkalis. CaO consumed SiO2, which was tightly bound to Fe2O3 in RM, and released Fe2O3, which promoted Fe leaching. RM-SCW showed the best desulfurization performance, which maintained 88.99 ± 0.0020% at 450 min, followed by RM-CaO-SW (450 min, 60.75 ± 6.00%) and RM (180 min, 88.52% ± 0.00068). The neutralization of alkaline components, the redox of metal oxides, and the liquid-phase catalytic oxidation of Fe contributed to the excellent desulfurization performance of the RM-SCW slurry. A promising approach shown in this study is beneficial to RM waste use, SO2 pollution control, and sustainable growth of the aluminum industry.

Study on the Role of Quartz in the Bio-Oxidation of Sulfide Minerals From Mine Solid Waste.

Sulfide-containing mine waste was oxidized to produce acid mine drainage, which lead to acidification of surrounding soil and downstream rivers and posed a threat to the surrounding environment. Quartz often coexists with sulfide minerals and affects the oxidation of sulfide minerals. In order to explore the role of quartz in the bio-oxidation of sulfide minerals in mine solid waste, the mixed minerals of quartz and sulfide minerals were bio-oxidized by Acidithiobacillus ferrooxidans. The results showed that quartz could improve the microbial activity and increase the acid production of sulfide minerals. The larger the proportion of quartz in bio-oxidation of sulfide minerals, the less the production of secondary minerals such as jarosite, and the larger the leaching amount of iron and sulfate. This research provides new ideas for speeding up the bio-oxidation of sulfide mineral to remove iron and sulfate. It provides a new way to solve acid pollution caused by oxidation of sulfide minerals.

Experimental and Model Predictive Investigation into the Relationship of pH Alternation with Addition of Lime in Acid Tin Tailing Treatments.

Lime is one of the commonly used amendments for acidic soils. The reasonable application of lime can effectively improve the current status of acid tailings and reduce harm to the environment. In this study, we analyzed the pH alternation of acid tin tailing as a function of lime dose based on three methods-single titration method, K-bicarbonate titration method, and buffer curve method-to predict the accurate lime requirement (LR) in acid tin tailing treatments. Of these prediction methods, the buffer curve method was best suited for the prediction of lime dose, and the prediction values agreed with the experimental data by factors of 1.0‒1.4. Thus, we determined that the buffer curve method was more suitable for predicting the lime requirement of acid tailings. This study of acid tailings lime requirement provides scientific research for the subsequent modification of tailings.

Study on Tailings Covering System Constructed by Geological Polymerization of Mine Waste, Part 1: Material Characterization and Cover Construction.

Acid mine drainage (AMD) is a serious and persistent environmental pollution problem. At present, many studies have focused on the tailings pond's cover systems. This paper introduced the research results of using tin tailings from Laili mountain to make the covering layer of tailings pond. The first part included a detailed description of tailings characterization and acid production potential. On this basis, the hard layer (HL) was prepared and its feasibility as oxidation barrier was evaluated. It was found that when the proportion of tailings waste was 70%, the immobilization efficiency of heavy metals can reach more than 99.45%, and the pH of leaching solution was about 10.8. Moreover, the beneficial effect of solid waste addition on the HL was also verified. This suggests that HL as a post-mining restorative strategy has strong positive influence on pollution control.

Formation Process of Silicate-Iron Oxyhydroxide Complex and Its Influence on the Distribution of Heavy Metals in Mining Area.

Silicate-iron oxyhydroxide complex formed by mineral weathering has an important influence on the geochemical reactions of heavy metals in mining areas. In this work, tailings were collected from an abandoned iron tailings pond, and the physicochemical properties and distribution of heavy metals were studied under natural weathering and hydraulic processes. The results showed that Fe2+ in the iron tailings were transported to the surface during the weathering process, and then the iron oxyhydroxide formed by mineralization adsorbed Cu2+ and Zn2+. Silicic acid and exchangeable acid were released during the formation of binary agglomerates between hydroxy iron oxide and kaolin, then they migrated to the lower area of a tailing pond via surface runoff. Finally, silicate-iron oxyhydroxide complex were formed. The heavy metals were replaced by H+ and penetrated to the bottom layer with water. This research provides an important scientific basis for the prevention and control of heavy metal pollution in mining areas.

Reversible Solubilization of Pyrene by a Gas Switchable Surfactant Investigated by Molecular Dynamics Simulation.

The reversible solubilization behavior of pyrene by a CO2/N2 switchable surfactant (named N'-dodecyl- N, N-dimethylacetamidinium bicarbonate (DDAB)) was investigated with molecular dynamics (MD) simulations. We first individually simulated the aggregation of the inactive surfactant N'-dodecyl- N, N-dimethylacetamidines (DDA) and effective surfactant DDAB in water. Detailed structural properties analysis showed that DDAB molecules aggregated into a micelle, while the aggregation of DDA molecules was considered to be an oil droplet that was separated from the water phase. MD simulations revealed that pyrene molecule was solubilized in the interior hydrophobic region of the micelle as expected. Pyrene was adsorbed on the surface of the oil droplet which is due to the dense packing of DDA molecules inside the oil droplet. The simulated release process showed that the solubilized pyrene in the interior was squeezed out when the micelle was changed to an oil droplet. Reduced density gradient (RDG) function was used to study the weak interactions and explore the molecular driving force behind the reversible solubilization. The results demonstrated that repulsion effects of water molecules on the DDA headgroups play an important role on the pyrene release. Because of the persistent molecular motion of DDA molecules into the droplet center, pyrene was finally repelled out of the oil droplet. Our study provided a molecular mechanism into the reversible solubilization of a gas-controlled switchable surfactant. This is expected to be useful for surfactant-enhanced remediation (SER) experiments.

Hydrogen cyanide catalytic hydrolysis mechanism by Al-doped graphene: A density functional theory study.

CONTEXT: The hydrogen cyanide (HCN) hydrolysis reaction mechanism over Al-doped graphene was investigated through the density functional theory method. HCN preferentially adsorbed vertically on the Al top site to form a stable adsorption configuration. H2O preferentially adsorbed parallel on the Al top site to form a stable adsorption configuration. The competitive adsorption of HCN and H2O weakened the adsorption stability of each molecule over Al-doped graphene. The break of C-N and H-O bonds was the key process in the preferential fracture pathway of the C-H bond. The break of C-N and C-H bonds was the key process in the preferential fracture pathway of the H-O bond. HCN played the role of bridge in the joint adsorption process. H atom transfer and C-N bond cleavage promoted the generation of CO and NH3. The change in the order of H atom transfer determined the reaction energy barrier. NH2CHO was more likely to act as an intermediate to promote the hydrolysis process. METHODS: The calculation work was achieved from the Dmol3 program in Material Studio 2017 using the GGA/PBE method with DNP basis, including the geometric structure and reaction pathway optimization, and adsorption energy calculation. All calculations were performed using a spin-polarized set and the TS method was used for DFT-D correction.

Improving the Rechargeable Li-CO2 Battery Performances by Tailoring Oxygen Defects on Li-Ni-Co-Mn Multi-Metal Oxide Catalysts Recycled from Spent Ternary Lithium-Ion Batteries.

Rechargeable Li-CO2 batteries are considered as a promising carbon-neutral energy storage technology owing to their ultra-high energy density and efficient CO2 capture capability. However, the sluggish CO2 reduction/evolution kinetics impedes their practical application, which leads to huge overpotentials and poor cyclability. Multi-element transit metal oxides (TMOs) are demonstrated as effective cathodic catalysts for Li-CO2 batteries. But there are no reports on the integration of defect engineering on multi-element TMOs. Herein, the oxygen vacancy-bearing Li-Ni-Co-Mn multi-oxide (Re-NCM-H3) catalyst with the α-NaFeO2-type structure is first fabricated by annealing the NiCoMn precursor that derived from spent ternary LiNi0.8Co0.1Mn0.1O2 cathode, in H2 at 300 °C. As demonstrated by experimental results and theory calculations, the introduction of moderate oxygen vacancy has optimized electronic state near the Fermi level (Ef), eventually improving CO2 adsorption and charge transfer. Therefore, the Li-CO2 batteries with Re-NCM-H3 catalyst deliver a high capacity (11808.9 mAh g-1), a lower overpotential (1.54 V), as well as excellent stability over 216 cycles at 100 mA g-1 and 165 cycles at 400 mA g-1. This study not only opens up a sustainable application of spent ternary cathode, but also validates the potential of multi-element TMO catalysts with oxygen defects for high-efficiency Li-CO2 batteries.

Mechanical insights into desulfurization by peroxymonosulfate oxidation via a non-reactive oxygen species pathway.

Air pollution by sulfur dioxide (SO2) remains a pressing concern for both the environment and human health. Desulfurization enhanced by persulfate based advanced oxidation processes (PS-AOPs) has been proven to be a feasible method. However, the inherent contradiction between the rapid diffusion mass transfer of SO2 in the "gas-liquid-gas" phase and the limited lifespan of reactive oxygen species (ROS) can not be ignored. Excessive investment in PS is required to sustainably generate ROS to achieve continuous desulfurization performance, which may lead to excessive PS consumption. To address this issue, whether PS can achieve the oxidation absorption of SO2 via a non-reactive oxygen species pathway was investigated. Experimental and computational results demonstrated that peroxymonosulfate (PMS) instead of peroxydisulfate (PDS) had a great SO2 removal performance, the utilization of PS could be effectively achieved by maintaining a 1:1 molar ratio of PMS and removed SO2. The presence of HOO bonds in the PMS introduced a partial positive charge to the oxygen atom, making the PMS polar and more susceptible to be attacked by the nucleophile HSO3-. So SO2 underwent a series of processes including dissolution, dissociation, one-oxygen atom transfer, and ionization before ultimately being converted into SO42- ions, effectively achieving its removal from flue gas. This study may presents a novel approach for achieving high-efficiency flue gas desulfurization.

Particulate polycyclic aromatic hydrocarbons in rural households burning solid fuels in Xuanwei County, Southwest China: occurrence, size distribution, and health risks.

The study is about the size distribution and health risks of polycyclic aromatic hydrocarbons (PAHs) in indoor environment of Xuanwei, Southwest China particle samples were collected by Anderson 8-stage impactor which was used to gather particle samples to nine size ranges. Size-segregated samples were collected in indoor from a rural village in Xuanwei during the non-heating and heating seasons. The results showed that the total concentrations of the indoor particulate matter (PM) were 757 ± 60 and 990 ± 78 µg/m3 in non-heating and heating seasons, respectively. The total concentration of indoor PAHs reached to 8.42 ± 0.53 µg/m3 in the heating season, which was considerably greater than the concentration in the non-heating season (2.85 ± 1.72 µg/m3). The size distribution of PAHs showed that PAHs were mainly enriched in PMs with the diameter <1.1 µm. The diagnostic ratios (DR) and principal component analysis (PCA) showed that coal and wood for residential heating and cooking were the main sources of indoor PAHs. The results of the health risk showed that the total deposition concentration (DC) in the alveolar region (AR) was 0.25 and 0.68 µg/m3 in the non-heating and heating seasons respectively. Throughout the entire sampling periods, the lifetime cancer risk (R) based on DC of children and adults varied between 3.53 ×10-5 to 1.79 ×10-4. During the heating season, the potential cancer risk of PAHs in adults was significant, exceeding 10-4, with a rate of 96%.

Exposure to O3 and NO2 on the interfacial chemistry of the pulmonary surfactant and the mechanism of lung oxidative damage.

Exposure to ozone (O3) and nitrogen dioxide (NO2) are related to pulmonary dysfunctions and various lung diseases, but the underlying biochemical mechanisms remain uncertain. Herein, the effect of inhalable oxidizing gas pollutants on the pulmonary surfactant (PS, extracted from porcine lungs), a mixture of active lipids and proteins that plays an important role in maintaining normal respiratory mechanics, is investigated in terms of the interfacial chemistry using in-vitro experiments; and the oxidative stress induced by oxidizing gases in the simulated lung fluid (SLF) supplemented with the PS is explored. The results showed that O3 and NO2 individually increased the surface tension of the PS and reduced its foaming ability; this was accompanied by the surface pressure-area isotherms of the PS monolayers shifting toward lower molecular areas, with O3 exhibiting more severe effects than NO2. Moreover, both O3 and NO2 produced reactive oxygen species (ROS) resulting in lipid peroxidation and protein damage to the PS. The formation of superoxide radicals (O2•-) was correlated with the decomposition of O3 and the reactions of O3 and NO2 with antioxidants in the SLF. These radicals, in the presence of antioxidants, led to the formation of hydrogen peroxide and hydroxyl radicals (•OH). Additionally, the direct oxidation of unsaturated lipids by O3 and NO2 further caused an increase in the ROS content. This change in the ROS chemistry and increased •OH production tentatively explain how inhalable oxidizing gases lead to oxidative stress and adverse health effects. In summary, our results indicated that inhaled O3 and NO2 exposure can significantly alter the interfacial properties of the PS, oxidize its active ingredients, and induce ROS formation in the SLF. The results of this study provide a basis for the elucidation of the potential hazards of inhaled oxidizing gas pollutants in the human respiratory system.

Remediation of Cr(VI)-contaminated soil using self-sustaining smoldering.

Self-sustaining smoldering is an emerging technology for nonaqueous-phase liquid remediation; however, it is rarely applied for Cr(VI)-contaminated soil treatment. In this study, self-sustaining smoldering using rice straw (RS) as a surrogate fuel was applied to remediate Cr(VI)-contaminated soil for the first time. Thirteen one-dimensional vertical smoldering experiments were conducted to investigate the effectiveness of the smoldering method and the effects of key experimental parameters on smoldering remediation performance. Smoldering was observed to be self-sustaining within the range of RS particle size from <0.16 to 2.00-4.00 mm, airflow from 0.2 to 1 m3/h, and Cr(VI)-impacted soil/RS ratios from 2:1 to 6:1. The Cr(VI)-contaminated soil was effectively remediated, which was confirmed by lowered Cr(VI) contents in the treated samples (decreased by 52.22-86.57%) and the elevated fraction of Cr oxidizable and residual form (increased by 1.14-3.30 and 2.97-4.00 times, respectively), compared to the control. The reducing gases (CO and CxHy) generated during the smoldering played a crucial role in the remediation process. The contents of available P and K in the remediated soil containing the remaining biochar and ash increased, thus improving soil reusability. Hence, this study shows that smoldering with RS as supplemental fuel is a promising Cr(VI)-contaminated soil management technique without supplying substantial external energy.

Advancing application of satellite remote sensing technologies for linking atmospheric and built environment to health.

Background: The intricate interplay between human well-being and the surrounding environment underscores contemporary discourse. Within this paradigm, comprehensive environmental monitoring holds the key to unraveling the intricate connections linking population health to environmental exposures. The advent of satellite remote sensing monitoring (SRSM) has revolutionized traditional monitoring constraints, particularly limited spatial coverage and resolution. This innovation finds profound utility in quantifying land covers and air pollution data, casting new light on epidemiological and geographical investigations. This dynamic application reveals the intricate web connecting public health, environmental pollution, and the built environment. Objective: This comprehensive review navigates the evolving trajectory of SRSM technology, casting light on its role in addressing environmental and geographic health issues. The discussion hones in on how SRSM has recently magnified our understanding of the relationship between air pollutant exposure and population health. Additionally, this discourse delves into public health challenges stemming from shifts in urban morphology. Methods: Utilizing the strategic keywords "SRSM," "air pollutant health risk," and "built environment," an exhaustive search unfolded across prestigious databases including the China National Knowledge Network (CNKI), PubMed and Web of Science. The Citespace tool further unveiled interconnections among resultant articles and research trends. Results: Synthesizing insights from a myriad of articles spanning 1988 to 2023, our findings unveil how SRMS bridges gaps in ground-based monitoring through continuous spatial observations, empowering global air quality surveillance. High-resolution SRSM advances data precision, capturing multiple built environment impact factors. Its application to epidemiological health exposure holds promise as a pioneering tool for contemporary health research. Conclusion: This review underscores SRSM's pivotal role in enriching geographic health studies, particularly in atmospheric pollution domains. The study illuminates how SRSM overcomes spatial resolution and data loss hurdles, enriching environmental monitoring tools and datasets. The path forward envisions the integration of cutting-edge remote sensing technologies, novel explorations of urban-public health associations, and an enriched assessment of built environment characteristics on public well-being.

Persulfate-based remediation of organic-contaminated soil: Insight into the impacts of natural iron ions and humic acids with complexation/redox functionality.

The use of persulfate (PDS) for in-situ chemical oxidation of organic contaminants in soils has garnered significant interest. However, the presence of naturally occurring iron-containing substances and humic acid (HA) in environmental compartments can potentially influence the effectiveness of soil remediation. Thus, this study aimed to investigate the role of key functional groups (adjacent phenolic hydroxyl (Ar-OH) and carboxyl groups (-COOH)) in HA that interact with iron. Modified HAs were used to confirm the significance of these moieties in iron interaction. Additionally, the mechanism by which specific functional groups affect Fe complexation and redox was explored through contaminant degradation experiments, pH-dependent investigations, HA by-products analysis, and theoretical calculations using six specific hydroxybenzoic acids as HA model compounds. The results showed a strong positive correlation between accessible Ar-OH and -COOH groups and Fe3+/Fe2+ redox. This was attributed to HA undergoing a conversion process to a semiquinone-containing radical form, followed by a quinone-containing intermediate, while Fe3+ acted as an electron shuttle between HA and PDS, with Fe3+ leaching facilitated by generated H+ ions. Although the stability of HA-Fe3+ complexes with -COOH as the primary binding sites was slightly higher at neutral/alkaline conditions compared to acidic conditions, the buffering properties of the soil and acidification of the PDS solution played a greater role in determining the Ar-OH groups as the primary binding site in most cases. Therefore, the availability of Ar-OH groups on HA created a trade-off between accelerated Fe3+/Fe2+ redox and quenching reactions. Appropriate HA and iron contents were found to favor PDS activation, while excessive HA could lead to intense competition for reactive oxygen species (ROS), inhibiting pollutant degradation in soil. The findings provide valuable insights into the interaction of HA and Fe-containing substances in persulfate oxidation, offering useful information for the development of in-situ remediation strategies for organic-contaminated soil.

Qualitative determination of volatile substances in different flavored cigarette paper by using headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) combined with chemometrics.

In order to investigate the difference of volatile substances among flavored cigarette paper, which are supplied by several manufacturers with different batches, the stability of the complex system of scented cigarette paper was analyzed and evaluated. In this study, Headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) was used to detect the aroma compounds of 23 flavored cigarette paper samples. Based on fingerprint analysis, the differences and changes of aroma compounds of different samples were studied in the form of data visualization. Principal component analysis, partial least squares regression analysis, cluster heatmap analysis and artificial neural network analysis were used to evaluate the stability of different cigarette paper. The results show that: A total of 29 volatile substances were identified from different scented cigarette paper. Fingerprint analysis revealed that the volatile substances of different cigarette paper samples were roughly the same, but not the content. The results of chemometrics analysis showed that there were significant differences in the characteristic aroma compounds of cigarette paper from different manufacturers. HS-GC-IMS technology combined with chemometrics method could be applied to determine the difference of volatile substances among different flavored cigarette paper, which theoretically and technically supported the quality stability maintenance and identification of flavored cigarette paper processed in different places.

Interactions between CuO NPs and PS: The release of copper ions and oxidative damage.

Copper oxide nanoparticles (CuO NPs) can adversely affect lung health possibly by inducing oxidative damage through the release of copper ions. However, the migration and transformation processes of CuO NPs in lung lining fluid is still unclear, and there are still conflicting reports of redox reactions involving copper ions. To address this, we examined the release of copper ions from CuO NPs in simulated lung fluid supplemented with pulmonary surfactant (PS), and further analyzed the mechanisms of PS-CuO NPs interactions and the health hazards. The results showed that the phospholipid of PS was adsorbed on the particle surface, which not only induced aggregation of the particles but also provided a reaction environment for the interaction of PS with CuO NPs. PS was able to promote the release of ions from CuO NPs, of which the protein was a key component. Lipid peroxidation, protein destabilization, and disruption of the interfacial chemistry also occurred in the PS-CuO NPs interactions, during which copper ions were present only as divalent cations. Meanwhile, the contribution of the particle surface cannot be neglected in the oxidative damage to the lung caused by CuO NPs. Through reacting with biomolecules, CuO NPs accomplished ion release and induced oxidative damage associated with PS. This research was the first to reveal the mechanism of CuO NPs releasing copper ions and inducing lipid oxidative damage in the presence of PS, which provides a new idea of transition metal-induced health risk in human body.

Inhibiting mechanisms of metal ion complexation on photogenerated reactive intermediates derived from dissolved black carbon.

Dissolved black carbon (DBC), an important photosensitizer in surface waters, can influence the photodegradation of various organic micropollutants. In natural water systems, DBC often co-occurs with metal ions as DBC-metal ion complexes; however, the influence of metal ion complexation on the photochemical activity of DBC is still unclear. Herein, the effects of metal ion complexation were investigated using common metal ions (Mn2+, Cr3+, Cu2+, Fe3+, Zn2+, Al3+, Ca2+, and Mg2+). Complexation constants (logKM) derived from three-dimensional fluorescence spectra revealed that Mn2+, Cr3+, Cu2+, Fe3+, Zn2+, and Al3+ quenched the fluorescence components of DBC via static quenching. The steady-state radical experiment suggested that in the complex systems of DBC with various metal ions, Mn2+, Cr3+, Cu2+, Fe3+, Zn2+ and Al3+ inhibited the photogeneration of 3DBC* via dynamic quenching, which reduced the yields of 3DBC*-derived 1O2 and O2·-. Moreover, 3DBC* quenching by metal ions was associated with the complexation constant. A strong positive linear relationship existed between logKM and the dynamic quenching rate constant of metal ions. These results indicate that the strong complexation ability of metal ions enabled 3DBC quenching, which highlights the photochemical activity of DBC in natural aquatic environments enriched with metal ions.

Vapour-liquid equilibrium relationship between toluene and mixed surfactants.

Micellar partitioning of volatile organic compounds (VOCs) in surfactant solutions and its effects on vapour-liquid equilibrium is fundamental to the overall design and implementation ofsurfactant-enhanced remediation. Knowledge of the vapour-liquid equilibrium partitioning coefficients for VOCs, especially in contaminated soils and groundwater in which they exist, is required. Headspace experiments were performed to quantify the effect of three mixed surfactants, cetyltrimethyl ammonium bromide (CTMAB) with tetrabutylammonium bromide (TBAB), sodium dodecyl sulphate (SDS) with Triton X-405 (TX405), and CTMAB with Triton X-100 (TX100), on the apparent Henry's constants (Hc) of toluene at temperatures ranging from 25 degrees C to 40 degrees C. The Hc values were significantly reduced in the presence of all three mixed surfactants at concentrations above their critical micelle concentrations (CMC). Mixed micellar partitioning, showing effects on the vapour-liquid equilibrium of toluene, was primarily responsible for the significant reduction of Hc in their mixed systems. The mixed surfactants CTMAB-TX100 had the greatest effect on Hc above the CMC, followed by SDS-TX405, then CTMAB-TBAB. Mixed systems of CTMAB-TX100 decreased Hc at concentrations significantly lower than the SDS-TX405 and CTMAB-TBAB concentrations, because of to the lower CMC of CTMAB-TX100. Vapour-liquid equilibrium data were also tested against the model (Hc = H/(1 + K(X - CMC)) that described the partitioning of VOCs in vapour-water-micelle phases. The correlation of Hc with mixed surfactant concentrations (X) and CMC can be utilized as an effective tool to predict the Hc by mixed surfactants.