ExtraCorporeal Membrane Oxygenation in the therapy for REfractory Septic shock with Cardiac function Under Estimated (ECMO-RESCUE): study protocol for a prospective, multicentre, non-randomised cohort study.

INTRODUCTION: Severe septic cardiomyopathy (SCM) is one of the main causes of refractory septic shock (RSS), with a high mortality. The application of venoarterial extracorporeal membrane oxygenation (ECMO) to support the impaired cardiac function in patients with septic shock remains controversial. Moreover, no prospective studies have been taken to address whether venoarterial ECMO treatment could improve the outcome of patients with sepsis-induced cardiogenic shock. The objective of this study is to assess whether venoarterial ECMO treatment can improve the 30-day survival rate of patients with sepsis-induced refractory cardiogenic shock. METHODS AND ANALYSIS: ExtraCorporeal Membrane Oxygenation in the therapy for REfractory Septic shock with Cardiac function Under Estimated is a prospective, multicentre, non-randomised, cohort study on the application of ECMO in SCM. At least 64 patients with SCM and RSS will be enrolled in an estimated ratio of 1:1.5. Participants taking venoarterial ECMO during the period of study are referred to as cohort 1, and patients receiving only conventional therapy without ECMO belong to cohort 2. The primary outcome is survival in a 30-day follow-up period. Other end points include survival to intensive care unit (ICU) discharge, hospital survival, 6-month survival, quality of life for long-term survival (EQ-5D score), successful rate of ECMO weaning, long-term survivors' cardiac function, the number of days alive without continuous renal replacement therapy, mechanical ventilation and vasopressor, ICU and hospital length of stay, the rate of complications potentially related to ECMO treatment. ETHICS AND DISSEMINATION: The trial has been approved by the Clinical Research and Application Institutional Review Board of the Second Affiliated Hospital of Guangzhou Medical University (2020-hs-51). Participants will be screened and enrolled from ICU patients with septic shock by clinicians, with no public advertisement for recruitment. Results will be disseminated in research journals and through conference presentations. TRIAL REGISTRATION NUMBER: NCT05184296.

Zinc promotes cell proliferation via regulating metal-regulatory transcription factor 1 expression and transcriptional activity in pulmonary arterial hypertension.

Metal responsive transcription factor 1 (MTF-1) is a zinc-dependent transcription factor involved in the development of pulmonary arterial hypertension (PAH), which is a life-threatening disease characterized by elevated pulmonary artery pressure and pulmonary vascular remodeling. However, little is known about the role and regulatory signaling of MTF-1 in PAH. This study aimed to investigate the effect and mechanism of MTF-1 on the proliferation of pulmonary arterial smooth muscle cells (PASMCs). Several techniques including intracellular-free zinc detected by fluorescent indicator-fluozinc-3-AM, western blot, luciferase reporter, and cell proliferation assay were conducted to perform a comprehensive analysis of MTF-1 in proliferation of PASMCs in PAH. Increased cytosolic zinc was shown in monocrotaline (MCT)-PASMCs and ZnSO4-treated PASMCs, which led to overexpression and overactivation of MTF-1, followed by the up-regulation of placental growth factor (PlGF). Elevated MTF-1 and PlGF were observed in western blot, and high transcriptional activity of MTF-1 was confirmed by luciferase reporter in ZnSO4-treated cells. Further investigation of cell proliferation revealed a favorable impact of zinc ions on PASMCs proliferation, with the deletion of Mtf-1/Plgf attenuating ZnSO4-induced proliferation. Flow cytometry analysis showed that blockade of PKC signaling inhibited the cell cycle of MCT-PASMCs and ZnSO4-treated PASMCs. The Zinc/PKC/MTF-1/PlGF pathway is involved in the up-regulatory effect on the PASMCs proliferation in the process of PAH. This study provided novel insight into zinc homeostasis in the pathogenesis of PAHs, and the regulation of MTF-1 might be a potential target for therapeutic intervention in PAH.

TNF-α contributes to sarcopenia through caspase-8/caspase-3/GSDME-mediated pyroptosis.

Sarcopenia has become a leading cause of disability and mortality in the elderly. It has been reported that programmed cell death (PCD) is associated with the development of sarcopenia that is characterized by reduction of muscle fiber size and number. TNF-α is also validated to play a prominent role in sarcopenia through its complex signaling pathways including cell death signaling. However, it is still unclear whether TNF-α contributes to sarcopenia by mediating pyroptosis, one type of PCD. Here, we first established naturally aged mice with sarcopenia model and confirmed an inflammatory state represented by TNF-α in aged mice. Evidence of GSDME-mediated pyroptosis and activation of apoptotic caspase-8/-3 were also found in skeletal muscle cells of aged mice with sarcopenia. We demonstrated that TNF-α triggered GSDME-mediated pyroptosis in myotubes through activating caspase-8 and caspase-3 by using caspase-8 and caspase-3 inhibitors. Comparing the activation of caspase-8 and GSDME expression between TNF Complex IIa and TNF Complex IIb, TNF-α was found to be more inclined to assemble TNF Complex IIb in activating caspase-8 and triggering pyroptosis. Moreover, pyroptotic myotubes were validated to result in decreased expression of MHC1 and finally loss of myotubes by knockdown of GSDME. Our work reveals a novel mechanism that TNF-ɑ/caspase-8/caspase-3/GSDME signaling-mediated pyroptosis contributes to the development of sarcopenia. Caspase-3/GSDME signaling-mediated pyroptosis may be a promising therapeutic target for sarcopenia.

Behavior of Sb and As in the hydrogeochemistry of adjacent karst underground river systems and the responses of such systems to mining activities.

Through the investigation of Qinglong mining area and adjacent karst underground river system, mining activities and water-rock interactions are found to control the hydrogeochemical evolution of karst underground water. Along the flow direction of the karst underground river, the hydro-chemical type is converted from HCO3-Ca type to SO4-Ca type. The concentrations of Sb and As also gradually decrease. Using PHREEQC to calculate the SI shows that: in the karst underground river system, both gypsum and fluorite are unsaturated, indicating a high degree of water-rock interaction. LogPCO2 is negatively correlated with pH, indicating that the karst underground river systems are both open systems. The dissolution of carbonate minerals and the alternate adsorption of ions are the main water-rock interactions that lead to the rapid decline of Sb and As concentrations. This research also applies principal component analysis to identify the types of pollution in adjacent karst underground river systems. The results show that the LongBaiwei underground river was mainly affected by coal mining activities, and Fe was more prominent; the ShuiYa underground river was more significantly affected by the leachate from the antimony tailings yard. This study provides a scientific basis for the evolution of the water environment as well as strategies for pollution prevention and control in typical karst underground river systems owing to the influence of mining activities.

Association Between Wait Time of Central Venous Pressure Measurement and Outcomes in Critical Patients With Acute Kidney Injury: A Retrospective Cohort Study.

Background: Hemodynamic management is of paramount importance in patients with acute kidney injury (AKI). Central venous pressure (CVP) has been used to assess volume status. We intended to identify the optimal time window in which to obtain CVP to avoid the incidence of adverse outcomes in patients with AKI. Methods: The study was based on the Medical Information Mart for Intensive Care (MIMIC) IV database. The primary outcome was in-hospital mortality. Secondary outcomes included the number of ICU-free days and norepinephrine-free days at 28 days after ICU admission, and total fluid input and fluid balance during the first and second day. A time-dose-response relationship between wait time of CVP measurement and in-hospital mortality was implemented to find an inflection point for grouping, followed by propensity-score matching (PSM), which was used to compare the outcomes between the two groups. Results: Twenty Nine Thousand and Three Hundred Thirty Six patients with AKI were enrolled, and the risk of in-hospital mortality increased when the CVP acquisition time was >9 h in the Cox proportional hazards regression model. Compared with 8,071 patients (27.5%) who underwent CVP measurement within 9 h and were assigned to the early group, 21,265 patients (72.5%) who delayed or did not monitor CVP had a significantly higher in-hospital mortality in univariate and multivariate Cox regression analyses. After adjusting for potential confounders by PSM and adjusting for propensity score, pairwise algorithmic, overlap weight, and doubly robust analysis, the results were still stable. The HRs were 0.58-0.72, all p < 0.001. E-value analysis suggested robustness to unmeasured confounding. Conclusions: Among adults with AKI in ICU, increased CVP wait time was associated with a greater risk of in-hospital mortality. In addition, early CVP monitoring perhaps contributed to shortening the length of ICU stays and days of norepinephrine use, as well as better fluid management.

The zinc transporter ZIP12 regulates monocrotaline-induced proliferation and migration of pulmonary arterial smooth muscle cells via the AKT/ERK signaling pathways.

BACKGROUND: The zinc transporter ZIP12 is a membrane-spanning protein that transports zinc ions into the cytoplasm from the extracellular space. Recent studies demonstrated that upregulation of ZIP12 is involved in elevation of cytosolic free zinc and excessive proliferation of pulmonary arterial smooth muscle cells (PASMCs) induced by hypoxia. However, the expression of ZIP12 and its role in pulmonary arterial hypertension (PAH) induced by monocrotaline (MCT) in rats have not been evaluated previously. The aim of this study was to investigate the effect of ZIP12 on the proliferation and migration of PASMCs and its underlying mechanisms in MCT-induced PAH. METHODS: A PAH rat model was generated by intraperitoneal injection of 20 mg/kg MCT twice at one-week intervals. PASMCs were isolated from the pulmonary arteries of rats with MCT-induced PAH or control rats. The expression of ZIP12 and related molecules was detected in the lung tissues and cells. A ZIP12 knockdown lentivirus and an overexpressing lentivirus were constructed and transfected into PASMCs derived from PAH and control rats, respectively. EdU assays, wound healing assays and Western blotting were carried out to explore the function of ZIP12 in PASMCs. RESULTS: Increased ZIP12 expression was observed in PASMCs derived from MCT-induced PAH rats. The proliferation and migration of PASMCs from PAH rats were significantly increased compared with those from control rats. These results were corroborated by Western blot analysis of PCNA and cyclin D1. All these effects were significantly reversed by silencing ZIP12. Comparatively, ZIP12 overexpression resulted in the opposite effects as shown in PASMCs from control rats. Furthermore, selective inhibition of AKT phosphorylation by LY294002 abolished the effect of ZIP12 overexpression on enhancing cell proliferation and migration and partially suppressed the increase in ERK1/2 phosphorylation induced by ZIP12 overexpression. However, inhibition of ERK activity by U0126 resulted in partial reversal of this effect and did not influence an increase in AKT phosphorylation induced by ZIP12 overexpression. CONCLUSIONS: ZIP12 is involved in MCT-induced pulmonary vascular remodeling and enhances the proliferation and migration of PASMCs. The mechanism of these effects was partially mediated by enhancing the AKT/ERK signaling pathways.

Zinc-mediated activation of CREB pathway in proliferation of pulmonary artery smooth muscle cells in pulmonary hypertension.

BACKGROUND: Transcription factor CREB is involved in the development of pulmonary hypertension (PH). However, little is known about the role and regulatory signaling of CREB in PH. METHODS: A series of techniques, including bioinformatics methods, western blot, cell proliferation and luciferase reporter assay were used to perform a comprehensive analysis of the role and regulation of CREB in proliferation of pulmonary artery smooth muscle cells (PASMCs) in PH. RESULTS: Using bioinformatic analysis of the differentially expressed genes (DEGs) identified in the development of monocrotaline (MCT)- and hypoxia-induced PH, we found the overrepresentation of CRE-containing DEGs. Western blot analysis revealed a sustained increase in total- and phosphorylated-CREB in PASMCs isolated from rats treated with MCT. Similarly, an enhanced and prolonged serum-induced CREB phosphorylation was observed in hypoxia-pretreated PASMCs. The sustained CREB phosphorylation in PASMCs may be associated with multiple protein kinases phosphorylated CREB. Additionally, hierarchical clustering analysis showed reduced expression of the majority of CREB phosphatases in PH, including regulatory subunits of PP2A, Ppp2r2c and Ppp2r3a. Cell proliferation analysis showed increased PASMCs proliferation in MCT-induced PH, an effect relied on CREB-mediated transcriptional activity. Further analysis revealed the raised intracellular labile zinc possibly from ZIP12 was associated with reduced phosphatases, increased CREB-mediated transcriptional activity and PASMCs proliferation. CONCLUSIONS: CREB pathway was overactivated in the development of PH and contributed to PASMCs proliferation, which was associated with multiple protein kinases and/or reduced CREB phosphatases and raised intracellular zinc. Thus, this study may provide a novel insight into the CREB pathway in the pathogenesis of PH. Video abstract.

Transcription factor CREB plays an important role in the development of pulmonary hypertension (PH). However, paradoxical roles have been reported in the pathogenesis of PH, and the regulatory mechanisms of CREB activation in pulmonary artery smooth muscle cells (PASMCs) proliferation remained unknown. In this study, we showed that CRE-containing genes were overrepresented among the differentially expressed genes in experimental PH, which resulted from the sustained activation of CREB pathway. The sustained activation of CREB pathway may be associated with the activation of multiple protein kinases that positively regulate CREB and down-regulation of numerous phosphatases involved in CREB dephosphorylation. Additionally, we found that the proliferation of PAMSCs was dependent on the CREB-mediated transcriptional activity in experimental PH. Moreover, the raised intracellular labile zinc possibly from ZIP12 may be associated with reduced protein phosphatases, increased CREB-mediated transcriptional activity and PASMCs proliferation. Collectively, we found CREB-mediated transcriptional activity in the proliferation of PASMCs in PH, which may be associated with multiple protein kinases and/or reduced phosphatases and elevated intracellular zinc. This study may reveal a critical role of zinc-mediated activation of CREB pathway in the proliferation of PASMCs, thus providing a more comprehensive understanding of CREB pathway in the pathogenesis of PH.

Association Between Preadmission Metformin Use and Outcomes in Intensive Care Unit Patients With Sepsis and Type 2 Diabetes: A Cohort Study.

Background: Sepsis is a deadly disease worldwide. Effective treatment strategy of sepsis remains limited. There still was a controversial about association between preadmission metformin use and mortality in sepsis patients with diabetes. We aimed to assess sepsis-related mortality in patients with type 2 diabetes (T2DM) who were preadmission metformin and non-metformin users. Methods: The patients with sepsis and T2DM were included from Medical Information Mart for Intensive Care -III database. Outcome was 30-day mortality. We used multivariable Cox regression analyses to calculate adjusted hazard ratio (HR) with 95% CI. Results: We included 2,383 sepsis patients with T2DM (476 and 1,907 patients were preadmission metformin and non-metformin uses) between 2001 and 2012. The overall 30-day mortality was 20.1% (480/2,383); it was 21.9% (418/1,907), and 13.0% (62/476) for non-metformin and metformin users, respectively. After adjusted for potential confounders, we found that preadmission metformin use was associated with 39% lower of 30-day mortality (HR = 0.61, 95% CI: 0.46-0.81, p = 0.007). In sensitivity analyses, subgroups analyses, and propensity score matching, the results remain stable. Conclusions: Preadmission metformin use may be associated with reduced risk-adjusted mortality in patients with sepsis and T2DM. It is worthy to further investigate this association.

Association between metformin use on admission and outcomes in intensive care unit patients with acute kidney injury and type 2 diabetes: A retrospective cohort study.

PURPOSE: Acute kidney injury (AKI) occurs in more than half of intensive care unit patients. Effective prevention and treatment strategies for AKI remain limited. We aimed to assess AKI-related mortality in patients with diabetes who were metformin and non-metformin users. MATERIALS AND METHODS: We included patients with AKI and type 2 diabetes (T2DM) from the Medical Information Mart for Intensive Care database. The 30-day mortality, neutrophil-to-lymphocyte ratio, and length of hospital stay were compared between patients with and without metformin prescriptions. We used multivariable Cox proportional hazards regression, propensity score analysis, and an inverse probability-weighting model to ensure the robustness of our findings. RESULTS: We included 4328 patients with AKI and T2DM (998 and 3330 patients were metformin and non-metformin users, respectively). The overall 30-day mortality was 14.2% (613/4328); it was 15.7% (523/3330) and 9.0% (90/998) for non-metformin and metformin users, respectively. In the inverse probability-weighting model, metformin use was associated with 37% lower 30-day mortality (HR = 0.63, 95% CI: 0.50-0.80, p < 0.0001). CONCLUSIONS: Metformin use may be associated with reduced risk-adjusted mortality in patients with AKI and T2DM. Further randomized controlled trials are needed to clarify this association.

Removal of PAHs at high concentrations in a soil washing solution containing TX-100 via simultaneous sorption and biodegradation processes by immobilized degrading bacteria in PVA-SA hydrogel beads.

Soil washing process enhanced by surfactants is a promising technique in removing organic pollutants from soil. In this work, a simultaneous sorption and biodegradation technique was used to remove 16 PAHs from a soil washing solution (SWS) obtained by rinsing a heavily contaminated soil from a coking plant with Triton X-100 (TX-100). This was done by immobilizing a pyrene-degrading bacterial strain in polyvinyl alcohol-sodium alginate (PVA-SA) hydrogel beads. Removal performance of free bacteria, blank PVA-SA beads and beads with immobilized degrading bacteria at a low, medium and high initial concentration was evaluated. The recycling and removal performance of the used beads were also examined. Our findings showed that hydrogel beads with immobilized bacteria at a medium concentration can remove around 77% ∑16PAHs from SWS in 96 h. The beads can be recycled and reused to treat a new SWS; 32-55% ∑16PAHs was removed in 24 h. The bead provided protection for bacteria against the co-existing substances such as TX-100. The bacteria-immobilized beads are more efficient and sustainable than free bacteria and blank beads due to simultaneous sorption and biodegradation processes, thus providing a solid reference for possible industrial application of bacteria immobilization technique to deal with SWSs with complex composition.

Relationship between high-normal albuminuria and arterial stiffness in Chinese population.

High-normal albuminuria is related to the morbidity and mortality of cardiovascular disease. Arterial stiffness has been regarded as a predictor of cardiovascular disease. However, the relationship between high-normal albuminuria and arterial stiffness is uncertain in Chinese population. A total of 1343 Chinese participants (aged 58.9 ± 12.1 years, 63.53% male) were included in this study. High-normal albuminuria was defined as urinary albumin-to-creatinine ratio (UACR) above the median within normal albuminuria. Based on the level of UACR, all participants were divided into low-normal albuminuria group (UACR < 6.36 mg/g, n = 580), high-normal albuminuria group (6.36 mg/g ≤ UACR < 30 mg/g, n = 581), microalbuminuria (30 mg/g ≤ UACR < 300 mg/g, n = 162), and macroalbuminuria (UACR ≥ 300 mg/g, n = 20). Arterial stiffness was assessed by measuring carotid-femoral pulse wave velocity (cfPWV). With the increment of UACR, the level of cfPWV was increased gradually (P < .001). Stepwise multiple regression analysis showed that systolic blood pressure, age, serum creatinine, heart rate, logarithmic (LG)-transformed UACR, and fasting plasma glucose were independently associated with cfPWV in all subjects (P < .001). LG-UACR was found to be related to cfPWV in high-normal albuminuria and macroalbuminuria subjects. After further stratification in the high-normal albuminuria subjects, their relation remained in male, elderly over 65 years old, or normotensives. In summary, UACR is associated with arterial stiffness in subjects with proteinuria excretion in high normal level. High-normal albuminuria might be an early indicator of arterial stiffness, especially in male, elderly, or normotensives in Chinese population. Furthermore, age and blood pressure are still observed to be the most important risk factor of arterial stiffness.

Chemical composition-dependent removal of cationic surfactants by carbon nanotubes.

How to attenuate water surfactant pollution using carbon nanomaterials (CNMs) has been gaining increasing research attention in recent years. However, how the composition of cationic surfactants and physicochemical properties of CNMs may affect cationic surfactant maximum removal efficiency (Refficiency-max) with minimal cost from the aqueous phase and the associated mechanisms remain largely unclear. To address this knowledge gap, we compared removal efficiency of three cationic surfactants including dodecyl dimethyl benzyl ammonium chloride (DDBAC), tetradecyl dimethyl benzyl ammonium chloride (TDBAC) and hexadecyltrimethylammonium bromide (CTAB) by various carbon nanotubes (CNTs), including pristine and OH- or COOH-functionalized multiwalled- (MWCNTs) and single-walled (SWCNTs) CNTs. The results showed that Refficiency-max of CTAB by pristine MWCNTs with an outer diameter OD < 8 nm is 50.36 ± 0.56%, while that by OH-MWCNTs with OD < 8 nm is merely 22.72 ± 0.21%. Surface area and porosity of CNTs strongly affect Refficiency-max of cationic surfactants. The MWCNTs with a smaller OD have a higher Refficiency-max than that with a larger one especially for CTAB, due to their larger surface area and porosity. Among various CNTs, SWCNTs is an ideal choice for removing cationic surfactants, especially for non-aromatic CTAB. Interestingly, for most cases, cationic surfactant removal by CNTs decreased when the amount of CNTs added exceeded a certain level, attributable to their aggregation. This implies that it is impossible to completely remove some cationic surfactants even when excess CNTs were added. The π-π bonding dominates over hydrophobic interaction in regulating cationic surfactant removal especially for those with aromatic structure. Aromatic cationic surfactants such as DDBAC and TDBAC can be removed more readily by CNTs than those without a benzene ring due to their strong π-π interactions. TDBAC has a longer hydrophobic chain relative to DDBAC, leading to a better removal efficiency by CNTs, due to stronger hydrophobic interaction.

Potential application of titanium dioxide nanoparticles to improve the nutritional quality of coriander (Coriandrum sativum L.).

TiO2 nanoparticles (nTiO2) have been widely used in many disciplines. However, whether they can be used to improve crops growth and nutritional quality is unknown. In this study, coriander (Coriandrum sativum L.) was treated with 0, 50, 100, 200, and 400 mg/L nTiO2 to evaluate their possible benefit to plant growth and nutritional quality under hydroponic conditions. Our observations showed that 50 mg/L nTiO2 only slightly but insignificantly increased the root and shoot fresh biomass by 13.2 % and 4.1 %, respectively, relative to the control. nTiO2 at this level promoted shoot K, Ca, Mg, Fe, Mn, Zn, and B accumulation, while spatial distribution of K, Ca, Fe, Mn, Cu and Zn in coriander leaves was not affected. No nTiO2 internalization or translocation to shoots occurred. 400 mg/L nTiO2 significantly reduced root fresh biomass by 15.8 % and water content by 6.7 %. Moreover, this high dose induced root cell membrane wrinkling, attributable to their aggregation and adsorption on root surfaces. At 100-400 mg/L, antioxidant defense systems (SOD, CAT and APX) in plant were triggered to alleviate oxidative stress. At an appropriate dose (50 mg/L), nTiO2 can improve nutrient quality of edible tissues without exerting toxicity to plant or posing health risk to consumers.

Effects of Various Carbon Nanotubes on Soil Bacterial Community Composition and Structure.

Carbon nanotubes (CNTs) have huge industrial potential, and their environmental impacts need to be evaluated. Knowledge of CNT impacts on soil microbial communities is still limited. To address this knowledge gap, we systematically examined dynamic effects of one type of single-walled carbon nanotubes (SWs) and three multiwalled carbon nanotubes (MWs) with different outer diameters on the soil bacterial community in an agricultural soil over 56 days. The results showed that SWs differently affected soil bacterial abundance, diversity, and composition as compared to MWs. The differences could have resulted from the materials' distinct physical structure and surface composition, which in turn affected their bioavailability in soil. For certain treatments, soil bacterial diversity and the relative abundance of certain predominant phyla were correlated with their exposure duration. However, many phyla recovered to their initial relative abundance within 56 days, reflecting resilience of the soil bacterial community in response to CNT-induced disturbance. Further analysis at the genus level showed differential tolerance to MWs, as well as size- and dose-dependent tolerance among bacterial genera. Predictive functional profiling showed that while CNTs initially caused fluctuations in microbial community function, community function largely converged across all treatments by the end of the 56 day exposure.

Plasma assisted-synthesis of magnetic TiO2/SiO2/Fe3O4-polyacrylic acid microsphere and its application for lead removal from water.

Hybrid microsphere of polyacrylic acid (PAA) grafted TiO2/SiO2/Fe3O4 (TSF-PAA) was synthesized via coating polyacrylic acid on the core-shell-shell TiO2/SiO2/Fe3O4 (TSF) structure with the aid of plasma technique. The synthesized microsphere was applied to remove Pb2+ from water. The state-of-the techniques including TEM, FTIP, TGA, and XPS were used to characterize the morphology and the surface functionalities of the microsphere and confirmed that PAA was successfully grafted on TSF surfaces and active functional groups were introduced. A combination of the BET, VSM, and XRD results showed that plasma treatment decreased surface area of TSF by 36%, whereas its magnetic property and crystalline structure were not significantly altered. Both the Pb2+-sorbed magnetic TSF and TSF-PAA can be separated with a magnet from the aqueous phase. The pH and dosage changes of the microspheres exerted an intense influence on their lead removal efficiency. Compared to TSF, the removal capacity of Pb2+ by TSF-PAA was considerably improved from 65% to 95%, attributable to the fact that PAA coating induced by plasma treatment additionally introduced carboxylic and hydroxyl groups to TSF. Their introduction greatly enhanced the interaction between Pb2+ and TSF-PAA relative to that with TSF, which had hydroxyl groups only as supported by XPS analysis.

A mechanistic study of stable dispersion of titanium oxide nanoparticles by humic acid.

Stable dispersion of nanoparticles with environmentally-friendly materials is important for their various applications including environmental remediation. In this study, we systematically examined the mechanisms of stable dispersion of two types of TiO2 nanoparticles (TNPs) with anatase and rutile crystalline structures by naturally occurring dissolved organic matter (humic acid) at different pHs, including at, below and above the Point of Zero Charge (PZC). The results showed that stable dispersion of TNPs by humic acid (HA) at all pHs tested can only be achieved with the assistance of ultra-sonication. The dispersion of TNPs by HA differed at the three pHs tested. Generally, HA greatly decreased the hydrodynamic diameters of TNPs at a very low concentration. The dispersion of TNPs became relatively stable when the HA concentration exceeded 5 mg/L, indicating that this HA concentration is required for stable dispersion of TNPs. The mechanisms involved in dispersion of TNPs by HA included electrostatic repulsion, steric hindrance and hydrophobic interaction. Electrostatic repulsion was identified to be the dominant mechanism. The dispersion of TNPs was enhanced when HA was added before ultra-sonication to avoid the partly irreversible re-aggregation of TNPs after sonication. The crystalline phases and concentrations of TNPs were also found to influence their stable dispersion. The findings from this work enhance understanding of the combined effects of HA, pH, ultra-sonication and crystalline structures of TNPs on their stable dispersion. The mechanisms identified can improve applications of TNPs in environmental water pollution control.

Association of 16 priority polycyclic aromatic hydrocarbons with humic acid and humin fractions in a peat soil and implications for their long-term retention.

To elucidate the environmental fate of polycyclic aromatic hydrocarbons (PAHs) once released into soil, sixteen humic acids (HAs) and one humin (HM) fractions were sequentially extracted from a peat soil, and sixteen priority PAHs in these humic substances (HSs) were analyzed. It was found that the total concentration of 16 PAHs (∑16PAHs) increased evidently from HA1 to HA16, and then dramatically reached the highest value in HM. The trend of ∑16PAHs in HAs relates to surface carbon and C-H/C-C contents, the bulk aliphatic carbon content and aliphaticity, as well as the condensation enhancement of carbon domains, which were derived from elemental composition, XPS, 13C NMR, as well as thermal analyses. HM was identified to be the dominant sink of 16 PAHs retention in soil, due to its aliphatic carbon-rich chemical composition and the highly condensed physical makeup of its carbon domains. This study highlights the joint roles of the physical and chemical properties of HSs in retention of PAHs in soil and the associated mechanisms; the results are of significance for PAH-polluted soil risk assessment and remediation.

Contamination characteristics and source apportionment of methylated PAHs in agricultural soils from Yangtze River Delta, China.

Alkylated PAHs (APAHs) have been shown to be more toxic and persistent than their non-alkylated parent compounds. However, little is known about the extent of soil contamination by these pollutants. To help understand agricultural soil pollution by these compounds at a regional scale, a total of 18 methylated PAHs (MPAHs, a major class of APAHs) in 243 soil samples were analyzed. These soil samples were collected from 11 sites in the Yangtze River Delta (YRD) region, a representative fast developing area in China. The total concentration of MPAHs (∑18MPAHs) ranged from 5.5 to 696.2 ng/g dry soil, with methylnaphthalenes (M-NAPs) and methylphenanthrenes (M-PHEs) accounting for more than 70% of the compositional profile. Relatively high concentrations of ∑18MPAHs were found in Jiaxing and Huzhou areas of Zhejiang province, as well as on the border between the cities of Wuxi and Suzhou. Different MPAH groups showed dissimilar spatial distribution patterns. The spatial distribution of lower molecular weight MPAHs was related to agricultural straw burning and emissions/depositions from industrial activities, whereas that of higher molecular weight MPAHs was much more a function of the total organic carbon (TOC) content of soil. Although coal, biomass (crop straw and wood), and petroleum combustion were identified to be the major emission sources for most of the sampling sites, the areas with relatively severe pollution with ∑18MPAHs resulted from the localized hotspots of petroleum leakage. Isomeric MPAHs with methyl group substituted at 2- (ß) position exhibited significantly higher concentrations than those substituted at 1- (α) position. Results of this work help to understand soil pollution by MPAHs, and are useful for designing effective strategies for pollution control so as to ensure food safety in areas with fast economic growth.

Sorption mechanisms of sulfamethazine to soil humin and its subfractions after sequential treatments.

Sorption mechanisms of an antibiotic sulfamethazine (SMT) to humin (HM) isolated from a peat soil and its subfractions after sequential treatments were examined. The treatments of HM included removal of ash, O-alkyl carbon, lipid, and lignin components. The HF/HCl de-ashing treatment removed a large amount of minerals (mainly silicates), releasing a fraction of hydrophobic carbon sorption domains that previously were blocked, increasing the sorption of SMT by 33.3%. The de-O-alkyl carbon treatment through acid hydrolysis greatly reduced polarity of HM samples, thus weakening the interaction between sorbents with water at the interfaces via H-bonding, leaving more effective sorption sites. Sorption of SMT via mechanisms such as van der Waals forces and π-π interactions was enhanced by factors of 2.04-2.50. After removing the lipid/lignin component with the improved Soxhlet extraction/acid hydrolysis, the organic carbon content-normalized sorption enhancement index Eoc was calculated. The results demonstrated that the Eoc-lipid for SMT (16.9%) was higher than Eoc-lignin (10.1%), implying that removal of unit organic carbon mass of lipid led to a higher increase in sorption strength than that of lignin. As each component was progressively removed from HM, the sorption strength and isotherm nonlinearity of the residual HM samples for SMT were gradually enhanced. The Koc values of SMT by HM samples were positively correlated with their aromatic carbon contents, implying that π-π electron donor-acceptor interactions between the benzene ring of sorbate and the aromatic domains in HM played a significant role in their interactions.

Surfactant removal with multiwalled carbon nanotubes.

The ability of multiwalled carbon nanotubes (MWCNTs) to remove a non-ionic surfactant, Triton X-100 (TX100), an anionic surfactant, sodium dodecylbenzenesulonate (SDBS), and a cationic surfactant, hexadecyltrimethylammonium bromide (CTAB) from the aqueous phase was investigated. Untreated, OH-, and COOH-functionalized MWCNTs with different outer diameters and chemical composition were examined and compared. As both the concentrations of surfactants and MWCNTs initially added may affect removal efficiency of surfactants, a relationship between the initial concentration ratio of surfactants and MWCNTs (Rc) and the removal efficiency (E) was established. The results showed that for a given Rc (e.g., 0.8), removal efficiency of the tested surfactants by a specific MWCNT (e.g., the untreated one with outer diameter <8 nm) decreased in the following order: TX100 (52.3%) > SDBS (26.2%) > CTAB (3.8%). TX100 was more readily removed by MWCNTs than SDBS and CTAB, due to its longer aliphatic chain compared to SDBS and CTAB thus higher hydrophobicity, and stronger π-π interactions with the aromatic structure of the surfaces of graphite sheets relative to CTAB. Based upon the established relationship between Rc and E of surfactants by MWCNTs, the maximum removal efficiency and the most appropriate Rc of TX100 and SDBS by two MWCNTs (UT8 and OH8) were derived. It was interesting to notice that, except for the case to remove TX100 using UT8, even though a large quantity of UT8 or OH8 was added to the TX100 or SDBS removal systems, they cannot be completely removed, with the maximum removal efficiency in the range of 55.88-87.17%. This mostly resulted from strong aggregation of MWCNTs thus reducing their readily accessible surface area and porosity for sorption.