Abstract In China, irrigation is widespread in 40.7% cropland to sustain crop yields. By its action on water cycle, irrigation affects water resources, and local climate. In this study, a new irrigation module, including flood and paddy irrigation technologies, was developed in the ORCHIDEE-CROP land surface model which describes crop phenology and growth in order to estimate irrigation demands over China from 1982 to 2014. Three simulations were performed including NI: no irrigation; IR: with irrigation limited by local water resources; and FI: with irrigation demand fulfilled. Observations and census data were used to validate the simulations. Results showed that the estimated irrigation water withdrawal (W) based on IR and FI scenarios bracket statistical W with fair spatial agreements (r = 0.68 ± 0.07; p < 0.01). Improving irrigation efficiency was found to be the dominant factor leading to the observed W decrease. By comparing simulated total water storage (TWS) with GRACE observations, we found that simulated TWS with irrigation well explained the TWS variation over China. However, our simulation overestimated the seasonality of TWS in the Yangtze River Basin due to ignoring regulation of artificial reservoirs. The observed TWS decrease in the Yellow River Basin caused by groundwater depletion was not totally captured in our simulation, but it can be inferred by combining simulated TWS with census data. Moreover, we demonstrated that land use change tended to drive W locally, but had little effect on total W over China due to water resources limitation.
{BACKGROUND: Globally, toxic metal exposures are a well-recognized risk factor for many adverse health outcomes. DNA methylation-based measures of biological aging are predictive of disease, but have poorly understood relationships with metal exposures. OBJECTIVE: We performed a pilot study examining the relationships of 24-h urine metal concentrations with three novel DNA methylation-based measures of biological aging: DNAmAge, GrimAge, and PhenoAge. METHODS: We utilized a previously established urine panel of five common metals [arsenic (As), cadmium (Cd), lead (Pb), manganese (Mn), and mercury (Hg)] found in a subset of the elderly US Veterans Affairs Normative Aging Study cohort (N = 48). The measures of DNA methylation-based biological age were calculated using CpG sites on the Illumina HumanMethylation450 BeadChip. Bayesian Kernel Machine Regression (BKMR) was used to determine metals most important to the aging outcomes and the relationship of the cumulative metal mixture with the outcomes. Individual relationships of important metals with the biological aging outcomes were modeled using fully-adjusted linear models controlling for chronological age, renal function, and lifestyle/environmental factors. RESULTS: Mn was selected as important to PhenoAge. A 1 ng/mL increase in urine Mn was associated with a 9.93-year increase in PhenoAge (95%CI: 1.24, 18.61
In this study, natural chalcopyrite (NCP) was employed in the activation of peroxymonosulfate (PMS) for bisphenol S (BPS) degradation. Firstly, the NCP catalyst was characterized via X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) techniques. Then, several key parameters such as catalyst dosage, PMS dosage and initial pH were investigated in NCP/PMS system. Furthermore, the transformation of various free radicals (SO4•−, •OH and O2•−) with the changes of initial pH were investigated by quenching experiments and electron spin resonance (ESR) study. Also, sulfur species cycling of copper and iron species were investigated via exogenous Cu2+ and Fe3+ addition experiments and X-ray photoelectron spectroscopy (XPS) analysis, the result indicated that sulfur species promoted Fe3+/Fe2+ and Cu2+/Cu+ cycles on the NCP surface. Furthermore, thirteen major degradation intermediates of BPS were detected by UPLC-QTOF-MS/MS and density functional theory (DFT) method was used to illustrate possible reaction pathways of BPS. Finally, a reasonable reaction mechanism of NCP/PMS system for BPS degradation was proposed on the basis of the comprehensive analysis. In brief, this work helps to provide useful information for the application of natural metallic sulfide minerals in treatment of contaminated waters.
Organic Matter (OM) with different molecular weight and functional groups can impact the adsorptive removal of metal ions, and the influence trend can be facilitated, inhibited or unchanged. However, the association capabilities of different ligands were superficially expounded. Based on the sorption behavior of Cr(III) onto titanate nanotubes (TNTs) with coexisting citric acid (CA), humic acid (HA) and fulvic acid (FA), this study highlighted differential absorbance and DFT simulations to quantitatively detect the mutual effect. As results, adsorption capacities of Cr(III) obviously enhanced from ca. 60 mg/g to 85 mg/g with CA or FA; while HA can slightly promote Cr(III) adsorption. UV spectra scanning proved that FA and HA led to the remarkable red shift of peak A1 (232 nm), A2 (262 nm), A3 (295 nm), A4 (431 nm) of Cr(III), and the area ratio of A2/A3 followed the order Cr-HA > Cr-FA > Cr-CA ≈ Cr. DFT calculations further confirmed that the simultaneous formation of ligand-metal-adsorbents complex and electrostatic effect promoted Cr(III) adsorption, with binding energies of −202.9 −420.8 kJ/mol and − 3958 kJ/mol, respectively. Meanwhile, the bridge connection of OM mainly appeared in the outer sphere of TNTs, as the larger molecular scale prevented their insertion into the inner spacing of TNTs, especially for HA and FA. Therefore, the adsorption mechanism was the combined actions of electrostatic attraction, bridge connection of OM and steric effect. This study can give insights into OM effects on metal adsorption, and quantificationally describe the junction state of ternary complex.