Pd/Cu bimetallic nano-catalyst supported on anion exchange resin (A520E) for nitrate removal from water: High property and stability.

High nitrate concentration in water can lead to eutrophication and the disruption of healthy aquatic ecosystems. Additionally, in the human digestive system, it has the potential to be reduced to nitrite, which can be damaging to people's physical health. Catalytic hydrogenation of nitrate is one of the strategies for removing nitrate from water. Using A520E resin as support, we prepared Pd/Cu nano-catalyst (Pd/Cu@A520E) according to a liquid phase reduction method. A520E could improve the transfer process of nitrate in the solution to the activity sites of Pd/Cu nanoparticles, thus increase the reaction rate of nitrate reduction. Pd/Cu bimetallic nano-particles were evenly distributed on/in the resin with a size range from 2 nm to 10 nm. The External Circulating System equipped with Venturi tube (ECSV) was designed to improve the utilization efficiency of H2 in both batch tests and long-term continuous-flow tests. Nearly 100% of nitrate removal efficiency and above 90% of N2 selectivity were achieved in both batch tests and continuous-flow tests. Coexisting Cl- and SO42- at 300 mg/L showed little impact on the property of Pd/Cu@A520E. Pd/Cu@A520E also showed high nitrate removal property and stability in continuous-flow tests of more than 800 h. NO3- was adsorbed onto the active sites (functional groups and Pd/Cu particle sites), meanwhile H2 was adsorbed onto the active sites of Pd/Cu@A520E to form Pd [H]. Then the adsorbed NO3- was reduced into N2 (main product) or NH4+ by Pd [H]. In addition, Pd/Cu@A520E showed high nitrate removal property from municipal waste water.

Electrocatalytic reduction of nitrate to ammonia by Pd/In modified Nickel foam electrode in aqueous solution.

Nitrate pollution in surface water and ground water has drawn wide attention, which has brought challenges to human health and natural ecology. Electroreduction of nitrate to NH3 in waste water was a way to turn waste into wealth, which has attracted interest of many researchers. Using Nickel foam as substrate, we prepared Pd/In bimetallic electrode (NF-Pd/In) according to a two-step electrodeposition method. There are many irregularly shaped particles in the size range of 10 nm-100 nm accumulated on the surface of prepared NF-Pd/In electrode, which could supply high specific area and more active sites for nitrate electroreduction. FESEM-EDS, XRD and XPS analysis confirmed the uniform distribution of Pd and In on the surface of prepared NF-Pd/In electrode, with a mass ratio of 4.5/1. Above 96% of 100 mg/L NO3--N was removed and 95% of NH3 selectivity was reached after 5 h of reaction under -1.6 V vs. Ag/AgCl sat. KCl when using 0.05 mol/L of Na2SO4 as electrolyte. High concentration of NaCl (0.05 mol/L) in the test solution dramatically decreased the NH3 selectivity because the produced NH3 could be further oxidized to N2 by the formed HClO from Cl-. EIS tests indicated that the prepared NF-Pd/In electrode showed much lower electrode resistance than NF due to the adsorptive property and electrocatalytic ability for nitrate removal. Density functional theory (DFT) calculations indicated that the presence of In could promote the conversion of NO3- to *NO3 during the process of nitrate electroreduction to NH3. Circulating tests demonstrated the stability of prepared NF-Pd/In electrode.

Enhanced remediation of Cr(VI)-contaminated groundwater by coupling electrokinetics with ZVI/Fe3O4/AC-based permeable reactive barrier.

Although widely used in permeation reaction barrier (PRB) for strengthening the removal of various heavy metals, zero-valent iron (ZVI) is limited by various inherent drawbacks, such as easy passivation and poor electron transfer. As a solution, a synergistic system with PRB and electrokinetics (PRB-EK) was established and applied for the efficient removal of Cr(VI)-contaminated groundwater. As the filling material of PRB, ZVI/Fe3O4/activated carbon (ZVI/Fe3O4/AC) composites were synthesized by ball milling and thermal treatment. A series of continuous flow column experiments and batch tests was conducted to evaluate the removal efficiency of Cr(VI). Results showed that the removal efficiency of Cr(VI) remained above 93% even when the bed volume (BV) reached 2000 under the operational parameters (iron/AC mass ratio, 2:1; current, 5 mA). The mechanism of Cr(VI) removal by the PRB-EK system was revealed through field emission scanning electron microscopy images, X-ray diffraction, X-ray photoelectron spectroscopy, Fe2+ concentration, and redox potential (Eh) values. The key in Cr(VI) reduction was the Fe2+/Fe3+ cycle driven by the surface microelectrolysis of the composites. The application of an externally supplied weak direct current maintained the redox process by enhancing the electron transfer capability of the system, thereby prolonging the column lifetime. Cr(VI) chemical speciation was determined through sequential extraction, verifying the stability and safety of the system. These findings provide a scientific basis for PRB design and the in-situ remediation of Cr(VI)-contaminated groundwater.

Tissue inhibitor of the metalloproteinases-3 gene polymorphisms and carotid plaque susceptibility in the Han Chinese population.

Tissue inhibitor of metalloproteinases (TIMPs) are endogenous inhibitors of matrix metalloproteinases that are involved in normal cellular processes and in the development and progression of atherosclerosis. Our purpose was to evaluate the polymorphisms of the TIMP-3 genes for their associations with carotid plaques or with serum protein levels in the Han Chinese population. Two promoter variants, -915A/G (rs2234921) and -1296T/C (rs9619311), were genotyped in 548 subjects with no plaques, 462 subjects with echogenic plaques, and 427 subjects with mixture plaques. The serum TIMP-3 levels were measured using an enzyme-linked immunosorbent assay (ELISA). There was a strong linkage disequilibrium between -1296T/C and -915A/G (D' = 1.0, r2 = 0.991). The individuals with the genotype (TC+CC) were 1.8 times more likely to have mixture plaques than the individuals with the TT genotype (P = 0.001, OR: 1.836, 95%CI: 1.269-2.665). The frequency of the C allele in the mixture plaque group was significantly higher than in the no plaque group (P = 0.009, CI: 1.119-2.187). We observed a significant elevation of the TIMP-3 levels in the serum of patients affected with mixture plaques compared to those with no plaques (P = 0.013). The current data suggest that genetic variation in the TIMP-3 genes may contribute to individual differences in mixture plaque susceptibility in the Han Chinese population.

[Association of ADAMTS-1 gene polymorphisms with ischemic stroke caused by large artery atherosclerosis].

OBJECTIVE: To assess the association of a disintegrin and metallo-proteinase with thrombospondin type 1 motifs (ADAMTS-1) gene polymorphism and ischemic stroke caused by large artery atherosclerosis (LAA). METHODS: In total 767 patients and 506 controls were recruited. Single nucleotide polymorphisms (SNPs) rs416905 (T/C) and rs402007 (G/C) of the ADAMTS-1 gene were genotyped by polymerase chain reaction and DNA sequencing. RESULTS: Frequencies of the rs402007 GC+CC genotype and the C allele were significantly different between the two groups (68.84% vs. 60.67%, χ2=9.012, P=0.003, OR=1.432; 45.24% vs. 38.54%, χ2=11.208, P=0.001, OR=1.318). Binary logistic regression has confirmed that the above difference was significant (P=0.001, OR=1.521, 95%CI: 1.183-1.955). The frequencies of TC+CC and GC+CC genotypes were similar between the two groups, and so was it with the C allele. The two SNPs had been in complete linkage disequilibrium (D'=1.0, r2=1.0). CONCLUSION: The rs416905 and rs402007 polymorphisms of the ADAMTS-1 gene may be associated with ischemic stroke caused by LAA. The C allele of the rs402007 locus may be a susceptibility factor for this subtype of stroke.

Nano-ZnO-modified hydroxyapatite whiskers with enhanced osteoinductivity for bone defect repair.

Hydroxyapatite (HA) whisker (HAw) represents a distinct form of HA characterized by its high aspect ratio, offering significant potential for enhancing the mechanical properties of bone tissue engineering scaffolds. However, the limited osteoinductivity of HAw hampers its widespread application. In this investigation, we observed HAw-punctured osteoblast membranes and infiltrated the cell body, resulting in mechanical damage to cells that adversely impacted osteoblast proliferation and differentiation. To address this challenge, we developed nano-zinc oxide particle-modified HAw (nano-ZnO/HAw). Acting as a reinforcing and toughening agent, nano-ZnO/HAw augmented the compressive strength and ductility of the matrix materials. At the same time, the surface modification with nano-ZnO particles improved osteoblast differentiation by reducing the mechanical damage from HAw to cells and releasing zinc ion, the two aspects collectively promoted the osteoinductivity of HAw. Encouragingly, the osteoinductive potential of 5% nano-ZnO/HAw and 10% nano-ZnO/HAw was validated in relevant rat models, demonstrating the efficacy of this approach in promoting new bone formation in vivo. Our findings underscore the role of nano-ZnO particle surface modification in enhancing the osteoinductivity of HAw from a physical standpoint, offering valuable insights into the development of bone substitutes with favorable osteoinductive properties while simultaneously bolstering matrix material strength and toughness.

Phenylurea herbicide degradation and N-nitrosodimethylamine formation under various oxidation conditions: Relationships and transformation pathways.

Four phenylurea herbicides (PUHs) were assessed for degradation and transformation into N-nitrosodimethylamine (NDMA) under three oxidation conditions (chlorine (Cl2), chlorine dioxide (ClO2), and ozone (O3)) from an aqueous solution. Removal ratios correlated with the numbers of halogen elements contained in PUHs (isoproturon (0) > chlorotoluron (1 Cl) > diuron (2 Cl) > fluometuron (3 F)), and the degradation efficiencies of oxidants from fastest to slowest were: O3, ClO2, and Cl2. NDMA can be generated directly from the ozonation of PUHs. Further, compared with chloramination alone, ozonation prominently promoted NDMA formation potential (NDMA-FP) during post-chloramination, and NDMA-FPs increased approximately 23-68 times than those during ozonation only at 2.5 mg/L O3 over 10 min; molar yields of NDMA from highest to lowest were 11.1% (isoproturon), 1.17% (chlorotoluron), 1.0% (diuron), and 0.73% (fluometuron). The PUH degradation kinetics data during ozonation agreed with the pseudo-first-order model. The rate constant kobs were 0.31 × 10-3-19.8 × 10-3 s-1. The kobs and removal ratios of PUHs during ozonation partially scaled with the mass, LogKow, and Henry's constants of PUHs. Comparisons of measured NDMA-FPs with calculated NDMA-FPs from residual PUH after oxidation showed that the intermediates produced during ozonation facilitated NDMA-FPs; this contribution was also observed for chlorotoluron and isoproturon during ClO2 oxidation. Examination of reaction mechanisms revealed that tertiary amine ozonation, N-dealkylation, hydroxylation, the cleavage of N-C bonds, ammonification, and nitrification occurred during the ozonation of PUHs, and the dimethylamine (DMA) functional groups could be decomposed directly and transformed into NDMA via the formation of the intermediate unsymmetrical dimethylhydrazine. NDMA is also formed from the reaction between DMA and phenylamino-compounds. Clarifying primary degradation products of PUHs and transformation pathways of NDMA during oxidation processes is useful to optimize treatment processes for water supplies.

Determination of N-nitrosodimethylamine in drinking water by UPLC-MS/MS.

The method for detecting N-nitrosodimethylamine (NDMA) in drinking water using ultra performance liquid chromatography (UPLC) coupled with tandem mass spectrometry (MS/MS) was improved by optimizing the clean-up procedure to remove the matrix interference in pretreatment process, and was then applied to a survey of NDMA in both raw and finished water samples from five water treatment plants in South China. The NDMA concentrations ranged from 4.7 to 15.1 ng/L in raw water samples, and from 4.68 to 46.9 ng/L in finished water. The NDMA concentration in raw water was found to be related with nitrite concentration, and during the treatment, the NDMA concentration increased following ozonation but decreased after subsequent activated carbon treatment.

Removal of multiple nitrosamines from aqueous solution by nanoscale zero-valent iron supported on granular activated carbon: Influencing factors and reaction mechanism.

Due to their significant absorption and reduction abilities, nanoscale zero-valent iron (nZVI)/granular activated carbon (GAC) composites are very effective for the degradation of organic contaminants and heavy metals. However, to date, there is no systematic study on the applicability of nZVI/GAC for the removal of multiple highly toxic nitrosamines from water supplies. For this study, nZVI/GAC was synthesized and applied to the degradation of multiple nitrosamines. The effects of initial nitrosamine concentration, composite dosage, contact duration, competition with coexistent elements, and reaction mechanisms during the nitrosamine removal process from aqueous solutions were investigated. Compared with bare nZVI and GAC, the removal rates of six nitrosamines via nZVI/GAC were initially very rapid. The highest removal ratios of the six nitrosamines were 76.1% (N-nitrosodimethylamine, NDMA), 84.7% (N-nitrosomethylethylamine, NMEA), 89.8% (N-nitrosodiethylamine, NDEA), 93.5% (N-nitrosodi-n-propylamine, NDPA), 95.7% (N-nitrosodi-n-butylamine, NDBA), and 80.4% (N-nitrosomorpholine, NMor). The nitrosamine degradation kinetics data agreed well with the pseudo-second-order model (R22 > 0.99), the rate constant k2 for nitrosamine (200 ng/L) removal by nZVI/GAC increased in the order of NDBA (0.3675) > NDPA (0.0254) > NMEA (0.0109) > NDEA (0.0105) > NDMA (0.0101) > NMor (0.0077). In the presence of cations, anions, and humic acid (HA) the removal of the six nitrosamines was inhibited at each concentration. Furthermore, the removal ratios and K2 of the five linear nitrosamines by nZVI/GAC partially scaled with structure, LogKow, and Henry's constant, particularly between K2 and these properties (R2 > 0.80). The reaction mechanism revealed that nitrosamines were adsorbed by GAC and then reduced by Fe0, where the reductive products were primarily secondary amines, nitrate, and nitrite. This study serves to improve our understanding, and further characterizes the removal of multiple nitrosamines by nZVI/GAC.

[Forms Distribution and Ecotoxicity of Three Forms of Sulfonamides in Root-Soil Interface of Maize].

Forms distribution and ecotoxicity of sulfonamides in root-soil interface of maize were studied by chemical analysis and luminescent bacteria toxicity assay. The results indicated that the water soluble residues were the main form in rhizosperic soils, and the organic solvent extractable residues were the main form in far-rhizosperic soils. The three forms of sulfonamides showed relatively lower toxicity to luminescent bacteria with the relative inhibition rates less than 30%. The toxicity of water soluble residues was lower than that of the organic solvent extractable residues, and the bound residues showed the lowest toxicity to luminescent bacteria. The contents and relative inhibition rates of water soluble residues in rhizosperic soils were higher than those in far-rhizosperic soils, while the contents and relative inhibition rates of organic solvent extractable and bound residues in rhizosperic soils were lower than those in far-rhizosperic soils.

Occurrence and profiling of multiple nitrosamines in source water and drinking water of China.

The occurrence of multiple nitrosamines was investigated in 54 drinking water treatment plants (DWTPs) from 30 cities across major watersheds of China, and the formation potential (FP) and cancer risk of the dominant nitrosamines were studied for profiling purposes. The results showed that N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA) and N-nitrosodi-n-butylamine (NDBA) were the most abundant in DWTPs, and the concentrations in source water and finished water samples were not detected (ND) -53.6ng/L (NDMA), ND -68.5ng/L (NDEA), ND -48.2ng/L (NDBA). The frequencies of detection in source waters were 64.8%, 61.1% and 51.8%, and 57.4%, 53.7%, and 37% for finished waters, respectively. Further study indicated that the FPs of the three main nitrosamines during chloramination were higher than those during chlorination and in drinking water. The results of Principal Components Analysis (PCA) showed that ammonia was the most closely associated factor in nitrosamine formation in the investigated source water; however, there was no significant correlation between nitrosamine-FPs and the values of dominant water-quality parameters. The advanced treatment units (i.e., ozonation and biological activated carbon) used in DWTPs were able to control the nitrosamine-FPs effectively after disinfection. The target pollutants posed median and maximum cancer risks of 2.99×10(-5) and 35.5×10(-5) to the local populations due to their occurrence in drinking water.

Characterization of the microbial community structure and nitrosamine-reducing isolates in drinking water biofilters.

Two biofilters were constructed using biological activated carbon (BAC) and nitrosamine-containing water from two drinking water treatment plants. The microbiome of each biofilter was characterized by 454 high-throughput pyrosequencing, and one nitrosamine-reducing bacterium was isolated. The results showed that nitrosamines changed the relative abundance at both the phylum and class levels, and the new genera were observed in the microbial communities of the two BAC filters after cultivation. As such, the genus Rhodococcus, which includes many nitrosamine-reducing strains reported in previous studies, was only detected in the BAC2 filter after cultivation. These findings indicate that nitrosamines can significantly affect the genus level in the microbial communities. Furthermore, the isolated bacterial culture Rhodococcus cercidiphylli A41 AS-1 exhibited the ability to reduce five nitrosamines (N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodi-n-propylamine, N-nitrosopyrrolidine, and N-nitrosodi-n-butylamine) with removal ratios that ranged from 38.1% to 85.4%. The isolate exhibited a better biodegradation ability with nitrosamine as the carbon source when compared with nitrosamine as the nitrogen source. This study increases our understanding of the microbial community in drinking water biofilters with trace quantities of nitrosamines, and provides information on the metabolism of nitrosamine-reducing bacteria.

Occurrence of nine nitrosamines and secondary amines in source water and drinking water: Potential of secondary amines as nitrosamine precursors.

Due to their high carcinogenicity, the control of nitrosamines, a group of disinfection by-products (DBPs), is an important issue for drinking water supplies. In this study, a method using ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry was improved for simultaneously analyzing nine nitrosamines in source water and finished water samples of twelve drinking water treatment plants (DWTPs) in China. The method detection limits of the nine target analytes were 0.2-0.9 ng/L for the source water samples and 0.1-0.7 ng/L for the finished water samples. Of the nine nitrosamines, six (N-nitrosodimethylamine (NDMA), nitrosodiethylamine (NDEA), N-nitrosomorpholine (NMor), N-nitrosodi-n-butylamine (NDBA), N-nitrosomethylethylamine (NMEA), and N-nitrosodiphenylamine (NDPhA)) were detected. The total nitrosamine concentrations in source water and finished water samples were no detection-42.4 ng/L and no detection-26.3 ng/L, respectively, and NDMA (no detection-13.9 ng/L and no detection-20.5 ng/L, respectively) and NDEA (no detection-16.3 ng/L and no detection-14.0 ng/L, respectively) were the most abundant. Meanwhile, the occurrence of nine secondary amines corresponding to the nine nitrosamines was also investigated. All of them except for di-n-propylamine were detected in some source water and finished water samples, and dimethylamine (no detection-3.9 µg/L and no detection-4.0 µg/L, respectively) and diethylamine (no detection-2.4 µg/L and no detection-1.8 µg/L, respectively) were the most abundant ones. Controlled experiments involving chloramination of four secondary amines confirmed that dimethylamine, diethylamine, morpholine and di-n-butylamine in water can form the corresponding nitrosamines, with diethylamine and morpholine showing significantly higher yields than dimethylamine which has already been identified as a precursor of NDMA. This study proved that diethylamine, morpholine and di-n-butylamine detected in raw water would be one of the important the precursors of NDEA, NMOR and NDBA, respectively, in drinking water.

Quantitative structure-activity relationship model for prediction of genotoxic potential for quinolone antibacterials.

Antibiotics are of concern because of their widespread usage, their potential role in the spread and maintenance of bacterial resistance, and because of the selection pressure on microbes. In this study, the genotoxic potential of 20 quinolone antibacterials, including 5 first-generation, 8 second-generation, and 7 third-generation quinolones, was determined. While all of the antibacterials studied showed genotoxic potential, the molar concentration for each antibacterial that produces 10% (EC10) of the maximum response of corresponding antibacterial ranged from 0.61 to 2917.0 nM, and was greatly dependent on chemical structures. A quantitative structure-activity relationship (QSAR) was established by applying a quantum chemical modeling method to determine the factors required for the genotoxic potential of quinolone antibacterials. The octanol-water coefficient (logP(ow)) adjusted bythe pH and energies of the highest occupied molecular orbital (epsilon(HOMO)) and lowest unoccupied molecular orbital (epsilon(LUMO)) were selected as hydrophobic and electronic chemical descriptors, respectively. The genotoxic potentials of quinolone antibacterials were found to be dependent on their logP(ow) and epsilon(HOMO), while the effects of epsilon(LUMO) on the genotoxic potentials could not be identified. The QSAR model was also used to predict the genotoxic potentials for 14 quinolone antibacterials, including 1 second-generation, 2 third-generation, and 11 fourth-generation quinolone antibacterials. A correlation between the genotoxic potentials and their minimal inhibition concentrations (MIC50) against Streptococcus pneumoniae from the literature for 18 quinolone antibacterials was observed, providing a potential method to estimate MIC50.