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Noncovalent interactions between fluoroquinolone antibiotics with dissolved organic matter: A 1H NMR binding site study and multi-spectroscopic methods
2019
Zhao, Xiating | Hu, Zhongzheng | Yang, Xing | Cai, Xuewei | Wang, Zhaowei | Xie, Xiaoyun
Fluoroquinolone antibiotics (FQs) are considered to be emerging environmental contaminants that have been detected extensively in aquatic environment. It is of quite importance to explore FQs interacting with dissolved organic matter (DOM). The interactions of FQs with DOM were examined by nuclear magnetic resonance (NMR) spectroscopy, fluorescence quenching, UV–vis, Fourier transform infrared (FT-IR) spectroscopic techniques. The bindings of FQs to DOM had one single binding site and their quenching mechanisms were static, which were evaluated by the Stern-Volmer and Site-binding equations. Addition of DOM could result in micro-environmental changes of fluorophores groups in FQs. The location adjacent oxygen right of Ofloxacin (OFL) and the aromatic ring (the adjacency replaced by two nitrogen-containing groups) of Ciprofloxacin (CIP), Enrofloxacin (ENR), Norfloxacin (NOR) might be highly affected by DOM molecule. The negative enthalpy change (ΔH⁰), negative entropy change (ΔS⁰) and the positive Gibbs' energy change (ΔG⁰) figured out that the binding processes were exothermic but not thermodynamic favorable, the formation of HA-FQs complexes would be powered chiefly by the ΔS⁰. H-bonding, electrostatic effect, van der Waals force were the acting force in the binding reactions and the π-π stacking effect was the major binding force under alkaline conditions. Moreover, the protonated, deprotonated, or partially protonated state of FQs were found to have different binding capacity to DOM, and the binding reactions for FQs-HA system were suppressed as the ionic strength increased. Meanwhile, alterations of FQs conformation in the presence of DOM were evaluated by FT-IR and UV–vis spectra.
Show more [+] Less [-]The association between short-term ambient air pollution and daily outpatient visits for schizophrenia: A hospital-based study
2019
Liang, Zhen | Xu, Chen | Cao, Yi | Kan, Hai-Dong | Chen, Ren Jie | Yao, Chun-Yan | Liu, Xiao-Ling | Xiang, Ying | Wu, Na | Wu, Long | Li, Ya-Fei | Ji, Ai-Ling | Cai, Tong-Jian
Schizophrenia is a devastating neuropsychiatric disorder with increasing concern. Limited studies have been conducted to assess the relationship between short-term exposure to ambient air pollution and schizophrenia attacks. This study aimed to investigate the associations between short-term air pollution exposure and schizophrenia outpatient visits based on a time-series study performed in China. Daily data of schizophrenia outpatient admissions and air pollution from 1 October 2010 to 31 December 2013 were collected in Xi'an, a heavily-polluted city in China. We utilized a time-series Poisson regression model to examine the associations between short-term air pollution and schizophrenia outpatient visits with different lag days. A total of 34,865 outpatient-visits for schizophrenia were identified. A 10 μg/m³ increase of PM₁₀, SO₂, and NO₂ concentrations corresponded to 0.289% (95% Cl: 0.118%, 0.460%), 1.374% (95% Cl: 0.723%, 2.025%), and 1.881% (95% Cl: 0.957%, 2.805%) elevation in outpatient-visits for schizophrenia at lag 0, and the associations appeared to be stronger, although not statistically significantly, in females and in middle and older age adults (40 and over). The most significant associations were observed on the concurrent day in different lag models. In conclusion, short-term exposure to ambient air pollution (PM₁₀, SO₂, and NO₂) can be associated with increased risk of daily outpatient visits for schizophrenia, which may contribute to the further understanding of the potential adverse effects of air pollution in schizophrenia and other neuropsychiatric disorders.
Show more [+] Less [-]Early life exposure to di(2-ethylhexyl)phthalate causes age-related declines associated with insulin/IGF-1-like signaling pathway and SKN-1 in Caenorhabditis elegans
2019
How, Chun Ming | Yen, Pei-Ling | Wei, Chia-Cheng | Li, Shang-Wei | Liao, Vivian Hsiu-Chuan
Di(2-ethylhexyl)phthalate (DEHP) is an ubiquitous and emerging contaminant that is widely present in food, agricultural crop, and the environment, posing a potential risk to human health. This study utilized the nematode Caenorhabditis elegans to decipher the toxic effects of early life exposure to DEHP on aging and its underlying mechanisms. The results showed that exposure to DEHP at 0.1 and 1.5 mg/L inhibited locomotive behaviors. In addition, DEHP exposure significantly shortened the mean lifespan of the worms and further adversely affected pharyngeal pumping rate and defecation cycle in aged worms. Moreover, DEHP exposure also further enhanced accumulation of age-related biomarkers including lipofuscin, lipid peroxidation, and intracellular reactive oxygen species in aged worms. In addition, exposure to DEHP significantly suppressed gene expression of hsp-16.1, hsp-16.49, and hsp-70 in aged worms. Further evidences showed that mutation of genes involved in insulin/IGF-1-like signaling (IIS) pathway (daf-2, age-1, pdk-1, akt-1, akt-2, and daf-16) restored lipid peroxidation accumulation upon DEHP exposure in aged worms, whereas skn-1 mutation resulted in enhanced lipid peroxidation accumulation. Therefore, IIS and SKN-1 may serve as an important molecular basis for DEHP-induced age-related declines in C. elegans. Since IIS and SKN-1 are highly conserved among species, the age-related declines caused by DEHP exposure may not be exclusive in C. elegans, leading to adverse human health consequences due to widespread and persistent DEHP contamination in the environment.
Show more [+] Less [-]Ozone exposure- and flux-yield response relationships for maize
2019
Peng, Jinlong | Shang, Bo | Xu, Yansen | Feng, Zhaozhong | Pleijel, Håkan | Calatayud, Vicent
A stomatal ozone (O₃) flux-response relationship for relative yield of maize was established by parameterizing a Jarvis stomatal conductance model. For the function (fVPD) describing the limitation of stomatal conductance by vapor pressure deficit (VPD, kPa), cumulative VPD during daylight hours was superior to hourly VPD. The latter function is proposed as a methodological improvement of this multiplicative model when stomatal conductance peaks during the morning and it is reduced later as it is the case of maize in this experiment. The model agreed relatively well with the measured stomatal conductance (R² = 0.63). Based on the comparison of R² values of the response functions, POD₆ (Phytotoxic Ozone Dose over an hourly threshold 6 nmol m⁻² s⁻¹) and AOT40 (accumulated hourly O₃ concentrations over a threshold of 40 ppb) performed similarly. The critical levels based on POD₆ and AOT40 for 5% reduction in maize yield were 1.17 mmol m⁻² PLA and 8.70 ppm h, respectively. In comparison with other important crops, the ranking of sensitivity of maize strongly differed depending on the O₃ metric used, AOT40 or POD₆. The newly proposed response functions are relevant for O₃ risk assessment for this crop in Asia.
Show more [+] Less [-]Combined spatial and retrospective analysis of fluoroalkyl chemicals in fluvial sediments reveal changes in levels and patterns over the last 40 years
2019
Mourier, B. | Labadie, P. | Desmet, M. | Grosbois, C. | Raux, J. | Debret, M. | Copard, Y. | Pardon, P. | Budzinski, H. | Babut, M.
Bed sediments and a dated sediment core were collected upstream and downstream from the city of Lyon (France) to assess the spatial and temporal trends of contamination by per- and polyfluoroalkyl substances (PFASs) in this section of the Rhône River. Upstream from Lyon, concentrations of total PFASs (ΣPFASs) in sediments are low (between 0.19 and 2.6 ng g⁻¹ dry weight - dw), being characterized by a high proportion of perfluorooctane sulfonate (PFOS). Downstream from Lyon, and also from a fluoropolymer manufacturing plant, ΣPFASs concentrations reach 48.7 ng g⁻¹ dw. A gradual decrease of concentrations is reported at the coring site further downstream (38 km). Based on a dated sediment core, the temporal evolution of PFASs is reconstructed from 1984 to 2013. Prior to 1987, ΣPFASs concentrations were low (≤2 ng g⁻¹ dw), increasing to a maximum of 51 ng g⁻¹ dw in the 1990s and then decreasing from 2002 to the present day (∼10 ng g⁻¹ dw). In terms of the PFAS pattern, the proportion of perfluoroalkyl sulfonic acids (PFSAs) has remained stable since the 1980s (∼10%), whereas large variations are reported for carboxylic acids (PFCAs). Long chain- (C > 8) PFCAs characterized by an even number of perfluorinated carbons represent about 74% of the total PFAS load until 2005. However, from 2005 to 2013, the relative contribution of long chain- (C > 8) PFCAs with an odd number of perfluorinated carbons reaches 80%. Such changes in the PFAS pattern likely highlight a major shift in the industrial production process. This spatial and retrospective study provides valuable insights into the long-term contamination patterns of PFAS chemicals in river basins impacted by both urban and industrial activities.
Show more [+] Less [-]Urban population exposure to tropospheric ozone: A multi-country forecasting of SOMO35 using artificial neural networks
2019
Antanasijević, Davor | Pocajt, Viktor | Perić-Grujić, Aleksandra | Ristic, Mirjana
Urban population exposure to tropospheric ozone is a serious health concern in Europe countries. Although there are insufficient evidence to derive a level below which ozone has no effect on mortality WHO (World Health Organization) uses SOMO35 (sum of means over 35 ppb) in their health impact assessments. Is this paper, the artificial neural network (ANN) approach was used to forecast SOMO35 at the national level for a set of 24 European countries, mostly EU members. Available ozone precursors’ emissions, population and climate data for the period 2003–2013 were used as inputs. Trend analysis had been performed using the linear regression of SOMO35 over time, and it has demonstrated that majority of the studied countries have a decreasing trend of SOMO35 values.The created models have made majority of predictions (≈60%) with satisfactory accuracy (relative error <20%) on testing, while the best performing model had R² = 0.87 and overall relative error of 33.6%. The domain of applicability of the created models was analyzed using slope/mean ratio derivate from the trend analysis, which was successful in distinguishing countries with high from countries with low prediction errors. The overall relative error was reduced to <14%, after the pool of countries was reduced based on the abovementioned criterion.
Show more [+] Less [-]Discovery of an arsenic and mercury co-elevation in the Midwest United States using reference laboratory data
2019
Day, Patrick L. | Nelson, Erik J. | Bluhm, Amy M. | Wood-Wentz, Christina M. | Jannetto, Paul J.
This study aimed to determine if there is a co-elevation of human blood arsenic and mercury levels in the Midwestern population of the United States (U.S.) and to determine any geographical patterns and variation of arsenic and mercury that may exist in Michigan. 58,800 blood specimens along with associated demographic/geographic data from the contiguous United States were reviewed. Univariate and multivariable logistic regression were used to analyze demographic/geographic variables associated with elevated arsenic concentrations. Furthermore, blood data from patients in Michigan were aggregated to the ZIP code tabulation area (ZCTA) in order to assess geographic variation using spatial regression models. SaTScan software was also used to analyze potential clustering of arsenic and mercury across Michigan ZCTAs. Within the contiguous United States, elevated mercury blood concentrations, older age, female sex, and coastal status were all associated with elevated arsenic blood concentrations (elevated mercury odds ratio (OR) 3.18 (3.04–3.33); female sex OR 1.06 (1.02–1.11); +10 yr age OR 1.12 (1.11–1.14); coastal state OR 1.33 (1.27–1.40). Within the state of Michigan, as with the continuous U.S., elevated mercury blood concentrations and older age were associated with elevated arsenic blood concentrations (elevated mercury OR 2.75 (2.38–3.18); female sex OR 1.06 (0.95–1.19); +10 yr age OR 1.10 (1.06–1.13). Using spatial regression, it was determined that within Michigan, economic inequality (measured via the Gini coefficient) was also associated with elevated concentrations of mercury in the blood. Clinical reference laboratory data, in conjunction with spatial analysis methods, may enhance our understanding of how elemental exposure affects human health and should be considered for studying how environmental contaminants, socioeconomics and geography affect the health of populations.
Show more [+] Less [-]Abiotic reduction of uranium(VI) with humic acid at mineral surfaces: Competing mechanisms, ligand and substituent effects, and electronic structure and vibrational properties
2019
Wang, Qian | Zhu, Chang | Huang, Xiaoxiao | Yang, Gang
Abiotic reduction represents an attractive technology to control U(VI) contamination. In this work, an abiotic route of U(VI) reduction with humic acid at mineral surfaces is proposed and reaction mechanisms are addressed by periodic density functional theory calculations. Different influencing factors such as ligand effect, content of CO₃²⁻ ligands and substituent effect are inspected. The coordination chemistry of uranyl(VI) surface complexes relies strongly on substrates and ligands, and the calculated results are in good agreements with experimental observations available. For the OH⁻ ligand, two competitive mechanisms co-exist that respectively produce the U(IV) and U(V) species, and the former is significantly preferred because of lower energy barriers. Instead, the NO₃⁻ ligand leads to the formation of U(V) while for the Cl⁻ ligand, the U(VI) surface complex remains very stable and is not likely to be reduced because of very high energy barriers. The U(V) and U(IV) complexes are the predominant products for low and high CO₃²⁻ contents, respectively. Accordingly, the abiotic reduction processes with humic acid are efficient to manage U(VI) contamination and become preferred under basic conditions or at higher CO₃²⁻ contents. The U(VI) reduction is further promoted by introduction of electron-donating rather than electron-withdrawing substituents to humic acid. Electronic structure analyses and vibrational frequency assignments are calculated for the various uranium surface complexes of the reduction processes, serving as a guide for future experimental and engineered studies. The molecular-level understanding given in this work offers an abiotic route for efficient reduction of U(VI) and remediation of U(VI)-contaminated sites at ambient conditions.
Show more [+] Less [-]Differences in quantity and composition of leaf particulate matter and morphological structures in three evergreen trees and their association in Harbin, China
2019
Xu, Haijun | Wang, Wenjie | Wang, Huimei | Sun, Yufeng | Zhong, Zhaoliang | Wang, Shurui
Urban trees have been assumed to effectively clean air particulate matter (PM), while the inter-species differences are not yet well defined, especially the PM chemical composition. In this study, PM from leaf surface and wax layer of 3 evergreen tree species (Juniper: Juniperus rigida; Black pine: Pinus tabuliformis var. mukdeais; Spruce: Picea koraiensis) were used for finding differences in PM adsorption and its compositional traits (characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectrum and Inductively coupled plasma-optical emission spectrometry). Possible improvement in PM removal was also evaluated by a detail whole city tree census and different scenarios of species adjustment data. We found that: 1) the amount of PM on juniper leaves was 5.73 g m−2, 2–2.5-fold higher than black pine and spruce (p < 0.05). Of them, 38.73%, 38.22%, and 23.11% were in the wax layer. 2) Compared with the explicit interspecies differences in PM quantity, more complex interspecies difference showed different patterns for different compositional traits. In general, leaf surface PM had higher O, Si, Al, Fe, N, Pb, Cu, Ni, Cr, and Cd, while the wax PM had higher C and Na contents (p < 0.05). 3) Association ordination found that the smaller leaf size, lower leaf water content, higher leaf area per unit mass, higher wax content, and larger stomatal openness aligned with the more PM adsorption by leaf, together with the higher amounts of CO stretching, O, Si, Al, N, heavy metals of Pb, Cu, Ni, Cr, and Cd in PM. 4) Compared with the other 2 species, increase of juniper percentage in urban forests is more effective for maximizing PM removal from air, accompanying more heavy metal removal but less crystalized minerals in PM. Our findings highlight that proper species configuration in urban afforestation could maximize the air PM removal capacity.
Show more [+] Less [-]Eight-year dry deposition of atmospheric mercury to a tropical high mountain background site downwind of the East Asian continent
2019
Phu Nguyen, Ly Sy | Zhang, Leiming | Lin, Da-Wei | Lin, Neng-Huei | Sheu, Guey-Rong
Atmospheric deposition, either dry or wet, has been identified as an important pathway of mercury (Hg) input to terrestrial and aquatic systems. Although East Asia is the major atmospheric Hg emission source region, very few studies have been conducted to quantify atmospheric Hg deposition in its downwind region. In this study, 8-year (2009–2016) atmospheric Hg dry deposition was reported at the Lulin Atmospheric Background Station (LABS), a high mountain forest site in central Taiwan. Dry deposition of speciated Hg was estimated using a bi-directional air-surface flux exchange model for gaseous elemental mercury (GEM) and dry deposition models for gaseous oxidized mercury (GOM) and particulate-bound mercury (PBM), making use of the monitored speciated atmospheric Hg concentrations. Annual total Hg dry deposition ranged from 51.9 to 84.9 μg m−2 yr−1 with a multi-year average of 66.1 μg m−2 yr−1. Among the three forms of atmospheric Hg, GEM was the main contributor to the total dry deposition, contributing about 77.8% to the total, due to the high density of forest canopy as well as the much higher concentration of GEM than GOM and PBM at LABS. Mercury dry deposition is higher in winter and spring than in summer and fall, partly due to the elevated Hg concentrations associated with air masses from East and Southeast Asia where with high atmospheric Hg emissions. The mean annual dry/wet deposition ratio of 2.8 at LABS indicated that Hg deposition to forest landscape was governed by dry rather than wet deposition.
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