Preferential segregation of gold at the symmetrical tilt grain boundaries of platinum: an atomic-scale quantitative understanding.

Grain boundary (GB) segregation plays a pivotal role in maintaining and optimizing the remarkable catalytic or mechanical properties of nanocrystalline Pt by reducing the Gibbs free energy and thereby impeding structure degradation. The solute segregation behavior at the Pt GB, however, is not well understood at the atomic level. In this study, we employed first-principles calculations to elucidate the preferential segregation behavior of a single Au atom at the symmetrical tilt GB of Pt. For pure Pt, a linear relationship between the GB energy and excess volume is observed. Therefore, Au exhibits strong segregation tendencies towards GB to release excess energy and volume stored at the strained GB. Although the segregation energy is sensitive to various GB sites, it is interesting to note that the minimum one increases linearly with GB energy. This site-sensitivity of segregation energy can be attributed to mechanical, chemical, and interaction parts, which are quantitatively related to the atomic volume, coordination number, and average bond length, respectively. Finally, the interplay among different structural descriptors is revealed. These insights into the association between GB structures, segregation configuration and energy offers valuable atomic-scale quantitative insights into the segregation behavior of Au in Pt GBs, which holds significant implications for the design of Pt nanomaterials with enhanced thermal stability via GB engineering.

Design and analysis of in-plane and out-of-plane heterostructures based on monolayer tri-G with enhanced photocatalytic property for water splitting.

Photocatalytic water splitting is considered to be a promising renewable solution to the energy crisis and environmental problems as an inexhaustible clean energy source. Graphene has an ultrahigh carrier mobility, but the zero gap limits its practical application in the photocatalysis field. Graphane has a wider band gap and retains a high carrier mobility, which demonstrates its great potential in this field. However, the broad band gap results in low photocatalytic efficiency. In this work, we propose two effective ways to modulate its electronic structure, modifying the structure of graphane and constructing a heterojunction using density functional calculations. We systematically investigated four trilayer graphane (tri-G) conformers and designed in-plane (lateral) and out-of-plane (vertical) heterojunctions with tri-G and chair-G (cha-G), the two most stable graphanes, with theoretical prediction. The results show that tri-G not only has a smaller band gap, falling in the ultraviolet range, which enhances the UV-light catalytic performance, but also has tunable band edge positions, locating outside the reduction potential of hydrogen and oxidation potential of water. Furthermore, the calculated electron effective mass for the tri-G conformers is smaller than that of cha-G. What's more, the band gap, band edge position, and photocatalytic efficiency are further optimized by constructing heterojunctions. In particular, both the in-plane and out-of-plane tri-G-C/cha-G heterostructures are confirmed as direct band gap semiconductors and type-I heterostructures exhibiting special band alignment, meanwhile satisfying the requirements for water splitting. And the band gaps of the heterostructures are further reduced. In addition, metal doping is expected to further optimize their electronic structure. These results provide theoretical support and a feasible modulation strategy for developing graphane as an effective photocatalyst for water splitting.

A double-cycle echo state network topology for time series prediction.

Echo state network (ESN) has gained wide acceptance in the field of time series prediction, relying on sufficiently complex reservoir connections to remember the historical features of the data and using these features to obtain the outputs by a simple linear readout. However, the randomness of its input and reservoir connections pose negative impacts on the prediction performance and performance stability of the models, the complexity of reservoir connections brings high time consumption during network computing, and the presence of randomness and complexity makes the hardware implementation of the ESN difficult. In response, we propose a double-cycle ESN (DCESN) based on the Li-ESN model, which has fixed weights to improve prediction performance and performance stability and simpler reservoir connections compared to the classical ESN to reduce the time consumption. The existence of both greatly reduces the difficulty of hardware implementation of the ESN and provides many conveniences for the future application of the ESN. Experimental results on many widely used time series datasets show that the DCESN has comparable or even better prediction performance than the ESN and good robustness against noise and parameter fluctuations.

High-performance Ruddlesden-Popper two-dimensional perovskite solar cells via solution processed inorganic charge transport layers.

Two-dimensional (2D) layered halide perovskites have been shown to enable improved long-term stability in comparison to the well-known three-dimensional hybrid organic-inorganic halide perovskites. The optoelectronic properties of the 2D perovskites are strongly influenced by the chemical nature of the charge transport layer. In this work, we fabricated Ruddlesden-Popper 2D perovskite solar cells (PSCs) using solution processed inorganic NiOx and a C60 : C70 (1 : 1) mixture as the hole and electron transport layers, which significantly improved the performance of the 2D PSCs. Time resolved photoluminescence measurements indicate the shortened lifetime of excitons, which demonstrates the excellent charge extraction properties. The PSCs based on these inorganic charge transport materials (CTMs) exhibit an average power conversion efficiency (PCE) of 14.1%, which is higher than that (12.3%) of PSCs using organic CTMs of poly(3,4-ethylenedioxythiophene) : poly(styrenesulfonate) (PEDOT:PSS) and phenyl-C61-butyric acid methyl ester (PCBM). Compared with PEDOT:PSS and PCBM based cases, the PSCs using inorganic CTMs also show improved long-term stability, with the PCE degradation significantly suppressed from 20% to 12% after a measurement of 15 days. The best PSCs using NiOx and C60 : C70 show a high PCE of 14.4%, with a stable power output and negligible hysteresis.

Synergistic engineering of shell thickness and core ordering to boost the oxygen reduction performance.

When benchmarked against the extended Pt(111), slightly weaker adsorption and stronger cohesion properties of surface Pt are required to improve activity and durability for the oxygen reduction reaction, respectively, making it challenging to meet both requirements on one surface. Here, using Pt(111) over-layers stressed and modified by Pt-TM (TM = Fe, Co, Ni, V, Cu, Ag, and Pd) intermetallics as examples, we theoretically identified ten promising catalysts by synergistically tailoring the skin thickness and substrate chemical ordering to simultaneously achieve weak adsorption and strong cohesion. More specifically, compared with Pt(111), all candidates exhibit 10-fold enhanced activity, half of which show improved durability, such as mono-layer skin on L12-Pt3Co or Pt3Fe, double-layer Pt on L13-Pt3Ni or Pt3Cu, and triple-layer skin on L11-PtCu, while double- or triple-layer skin on L10-PtCo or PtNi and double-layer skin on L12-PtFe3 show slightly poor durability. Although L10 and L12 based nanocrystals have been demonstrated extensively as outstanding catalysts, L11 and L13 ones hold great application potential. The coexistence of high activity and durability on the same surface is because of the different responses of surface adsorption and cohesion properties to the strain effects and ligand effects. When intermetallic-core@Pt-shell nanocrystals are constructed using this slab model, the necessity of protecting or eliminating low-coordinated Pt and the possibility of maximizing Pt(111) facets and core ordering by morphology engineering were highlighted. The current discovery provides a new paradigm toward the rational design of promising cathodic catalysts.

Facile synthesis of a novel BaSnO3/MXene nanocomposite by electrostatic self-assembly for efficient photodegradation of 4-nitrophenol.

Photocatalysis is regarded as one of the most effective strategies for the removal of the toxic organic pollutants from aqueous solutions. However, a lack of the efficient photocatalysts prevents the widespread practical application. Herein, the electrostatic self-assembly method has been designed for facile synthesis of a novel BaSnO3/PDDA/MXene (BSO/P/MX) nanocomposite as high efficient photocatalyst. In this nanocomposite, the BaSnO3 (BSO), poly (dimethyl-diallylammonium chloride) (PDDA) and MXene (Ti3C2Tx) act as the active species, structure stabilizer and efficient electron transfer medium, respectively. Due to the strong synergy of the nanocomposite, the electron-transferring ability as well as the charge separation efficiency is boosted and thus high catalytic activity achieves towards the photodegradation of 4-nitrophenol. The superior degradation rate of 98.8% and a rate constant K of 0.09113 min-1 have been realized within 75 min of ultraviolet (UV) light irradiation over the BSO/P/MX-8% catalyst. This as-prepared nanocomposite with the excellent catalytic activity can be employed as a promising photocatalyst for treating the organic pollutants from aqueous solutions.

Computational and solubility equilibrium experimental insight into Ca2+-fluoride complexation and their dissociation behaviors in aqueous solutions: implication for the association constant measured using fluoride ion selective electrodes.

Although the Ca2+-F- association is of great importance for aqueous environments and industrial systems containing F-, as well as for defluorination processes, many details of the association solvation structures and behavior remain unclear. Herein, a combination of classical/ab initio molecular dynamics simulations and density functional theory calculations was used to investigate the structure and hydration of CaFx2-x (x = 1, 2) and the association/dissociation behavior of Ca2+-F- in aqueous CaF2 solutions. The primary shell of Ca2+ is found to be very flexible in the association of Ca2+-F-, with coordination numbers dynamically oscillating in the range of 6-9, with 6 and 7 being the most favorable. The calculations show that for CaF(H2O)14+, the contact ion pair (CIP) is more favorable and occurs with no energy barrier, whereas the formation of CaF2(aq.) must overcome a ∼3.6 kJ mol-1 energy barrier; moreover, the CIP and solvent shared ion pair (SSIP) dynamically coexist for CaF2(H2O)14 in aqueous CaF2 solutions. Calculations for the dissociation process of CaF(H2O)6+ show a dramatic energy increase going from SSIP to free Ca2+ and F-, ascribed to the surprisingly long-range electrostatic attraction between Ca2+ and F- rather than to special F⋯H interactions. The energy increase results in the estimated association constant of CaF+ being larger than that previously measured using fluoride ion selective electrodes. This is attributed to the fact that the latter value might correspond to the ligand reaction of free Ca2+ and F- to form the Ca2+-F- SSIP. The combination of these results with CaF2(s) solubility measurements suggests that the higher-order Ca2+-F- complexes are absent in aqueous CaF2 solutions.

A spectroscopic study of solvent effects on the formation of Cu(ii)-chloride complexes in aqueous solution.

A combination of electronic (UV-vis) and X-ray absorption (EXAFS, XANES) spectroscopies has been used to investigate the formation of copper(ii)/chloride complexes in concentrated aqueous solutions. It is established that lowering the water activity by the addition of Mg(ClO4)2 at a constant Cl-/Cu(ii) ratio results in the replacement of water molecules by Cl- ions in the primary coordination shell of Cu(ii). This behavior closely parallels the effect of increasing the Cl-/Cu(ii) ratio and demonstrates that full understanding of the stoichiometry and structures of the complexes formed in concentrated metal-ion chloride solutions requires explicit consideration of the role of the solvent.

Rational Design of Sb@C@TiO2 Triple-Shell Nanoboxes for High-Performance Sodium-Ion Batteries.

Antimony is an attractive anode material for sodium-ion batteries (SIBs) owing to its high theoretical capacity and appropriate sodiation potential. However, its practical application is severely impeded by its poor cycling stability caused by dramatic volumetric variations during sodium uptake and release processes. Here, to circumvent this obstacle, Sb@C@TiO2 triple-shell nanoboxes (TSNBs) are synthesized through a template-engaged galvanic replacement approach. The TSNB structure consists of an inner Sb hollow nanobox protected by a conductive carbon middle shell and a TiO2 -nanosheet-constructed outer shell. This structure offers dual protection to the inner Sb and enough room to accommodate volume expansion, thus promoting the structural integrity of the electrode and the formation of a stable solid-electrolyte interface film. Benefiting from the rational structural design and synergistic effects of Sb, carbon, and TiO2 , the Sb@C@TiO2 electrode exhibits superior rate performance (212 mAh g-1 at 10 A g-1 ) and outstanding long-term cycling stability (193 mAh g-1 at 1 A g-1 after 4000 cycles). Moreover, a full cell assembled with a configuration of Sb@C@TiO2 //Na3 (VOPO4 )2 F displays a high output voltage of 2.8 V and a high energy density of 179 Wh kg-1 , revealing the great promise of Sb@C@TiO2 TSNBs as the electrode in SIBs.

TNNC1 Reduced Gemcitabine Sensitivity of Nonsmall-Cell Lung Cancer by Increasing Autophagy.

BACKGROUND As we know, chemotherapy resistance is a critical factor leading to recurrence and metastasis of nonsmall-cell lung cancer (NSCLC). To clarify the key target and potential mechanism of resistance to gemcitabine (GEM) in NSCLC, we selected Gene Expression Omnibus Data Set and statistically analyzed a parent cell group and a GEM-resistant cell group. Results showed that the expression of troponin C1, slow skeletal and cardiac type (TNNC1) in GEM-resistant cells was higher than in parent cells, which implies that TNNC1 was associated with GEM resistance in lung cancer cells. MATERIAL AND METHODS TNNC1 expression level was detected by reverse transcription-quantitative polymerase chain reaction or western blot in GEM-resistant patient serum and cell lines. It could reduce or increase autophagy response and GEM resistance accordingly by inhibition of the short interfering ribonucleic acid or by forced overexpression of TNNC1 viruses in A549 cell line and GEM-resistant cell line (A549/GemR) respectively. Blocking autophagy with 3-methyladenine increased the sensitivity of chemotherapy confirmed by flow cytometry and microtubule-associated protein 1A/1B - light chain 3 punctate assay. What's more, in a loss-of-function model, silencing of forkhead box 03 (FOXO3) in A549/GemR cells could rescue the autophagy weakened by TNNC1. RESULTS TNNC1 promoted GEM chemoresistance of NSCLC by activating cytoprotective autophagy, regulated negatively by FOXO3. This research may provide a completely new strategy for NSCLC treatment. CONCLUSIONS Targeting the TNNC1/FOXO3 signaling pathway in NSCLC may be a novel strategy to combat GEM resistance.

Intrinsic strain-induced segregation in multiply twinned Cu-Pt icosahedra.

We present an atomistic simulation study on the compositional arrangements throughout Cu-Pt icosahedra, with a specific focus on the effects of inherent strain on general segregation trends. The coexistence of radial and site-selective segregation patterns is found in bimetallic nanoparticles for a broad range of sizes and compositions, consistent with prior analytical and atomistic models. Through a thorough comparison between the composition patterns and strain-related patterns, it is suggested that the presence of gradient and site-selective segregation is natural to largely relieve the inherent strain by preferential segregation of big atoms at tensile sites and vice versa, as previously hypothesized in the literature. Analogous to the case of single crystal particles, Cu-rich surface and damped oscillations can also be found in the outer shells of icosahedra, which are dominated by the lowering of both the surface energy and the chemical energy. The thermodynamic stability of segregated icosahedra is similar to segregated cuboctahedra but higher than disordered bulk alloys, validating prior thinking that element segregation driven by strain relief can extend the stability range of multiply-twinned nanoparticles. Our work sheds new light on understanding strain-induced segregation in multiply-twinned nanosystems that have elements with large lattice mismatch and strong alloying ability.

Control of Charge Recombination in Perovskites by Oxidation State of Halide Vacancy.

Advances in perovskite solar cells require development of means to control and eliminate the nonradiative charge recombination pathway. Using ab initio nonadiabatic molecular dynamics, we demonstrate that charge recombination in perovskites is extremely sensitive to the charge state of the halogen vacancy. A missing iodine anion in MAPbI3 has almost no effect on charge losses. However, when the vacancy is reduced, the recombination is accelerated by up to 2 orders of magnitude. The acceleration occurs due to formation of a deep hole trap in the singly reduced vacancy, and both deep and shallow hole traps for the doubly reduced vacancy. The shallow hole involves a significant rearrangement of the Pb-I lattice, leading to a new chemical species: a Pb-Pb dimer bound by the vacancy charge, and under-coordinated iodine bonds. Hole trapping by the singly reduced iodide vacancy operates parallel to recombination of free electron and hole, accelerating charge losses by a factor of 5. The doubly reduced vacancy acts by a sequential mechanism-free hole, to shallow trap, to deep trap, to free electron, and accelerates the recombination by a factor of 50. The study demonstrates that iodine anion vacancy can be beneficial to the performance, because it causes minor changes to the charge carrier lifetime, while increasing charge carrier concentration. However, the neutral iodine and iodine cation vacancies should be strongly avoided. The detailed insights into the charge carrier trapping and relaxation mechanisms provided by the simulation are essential for development of efficient photocatalytic, photovoltaic, optoelectronic and related devices.

Health risk assessment of heavy metals and bacterial contamination in drinking water sources: a case study of Malakand Agency, Pakistan.

Human beings are frequently exposed to pathogens and heavy metals through ingestion of contaminated drinking water throughout the world particularly in developing countries. The present study aimed to assess the quality of water used for drinking purposes in Malakand Agency, Pakistan. Water samples were collected from different sources (dug wells, bore wells, tube wells, springs, and hand pumps) and analyzed for different physico-chemical parameters and bacterial pathogens (fecal coliform bacteria) using standard methods, while heavy metals were analyzed using atomic absorption spectrophotometry (AAS-PEA-700). In the study area, 70 % of water sources were contaminated with F. coliform representing high bacterial contamination. The heavy metals, such as Cd (29 and 8 %), Ni (16 and 78 %), and Cr (7 %), exceeded their respective safe limits of WHO (2006) and Pak-EPA (2008), respectively, in water sources, while Pb (9 %) only exceeded from WHO safe limit. The risk assessment tools such as daily intake of metals (DIMs) and health risk indexes (HRIs) were used for health risk estimation and were observed in the order of Ni > Cr > Mn > Pb > Cd and Cd > Ni > Pb > Mn > Cr, respectively. The HRI values of heavy metals for both children and adults were <1, showing lack of potential health risk to the local inhabitants of the study area.

[Simultaneous determination of four N-lauryl amino acid surfactants in facial cleansers by high performance liquid chromatography-ultraviolet detection].

Significant developments have recently been achieved in the field of N-lauryl amino acid (NLAA) surfactants derived from renewable resources. Compared with conventional surfactants, NLAAs exhibit remarkable surfactant properties, exceptional biodegradability, good biocompatibility, and high safety profiles. These attributes have led to the widespread use of NLAAs in personal-care products. The detection methods employed for NLAAs include two-phase titration (TT), spectrophotometric analysis (SA), and high performance liquid chromatography (HPLC). However, because both TT and SA measure the total concentration of anionic active matter, identifying and quantifying individual compounds in a sample containing multiple anionic surfactants is impossible. The presence of cationic surfactants in the sample also introduces interferences, which lead to significant errors. Compared with TT and SA, HPLC offers direct and rapid testing procedures. However, compounds with no or weak UV-visible light absorption exhibit low sensitivity when detected by UV, necessitating the use of detectors such as differential refractive index detectors (RIDs), evaporative light scattering detectors (ELSDs), or charged aerosol detectors (CADs). Most HPLC users consider UV light as the fundamental configuration of the instrument, and other detectors are less commonly employed. Therefore, establishing a new HPLC method suitable for the UV detection of NLAAs is of practical significance. In this study, a novel HPLC-UV method was developed for the simultaneous detection of N-lauryl glutamine (LG), N-lauryl glycine (LC), N-lauryl alanine (LA), and N-lauryl sarcosine (LS) by optimizing the mobile-phase composition and selecting an appropriate chromatographic column and detection wavelength. The samples were mixed with acetonitrile-0.10% H3PO4 aqueous solution (60∶40, v/v) and sonicated for 10 min, then stayed at room temperature for 5 min. Subsequently, the mixture was filtered through a 0.22 µm filter membrane and separated on an Agilent Eclipse Plus C18 column (150 mm×4.6 mm, 5 µm). The mobile phase used for separation consisted of acetonitrile-0.10% H3PO4 aqueous solution at a flow rate of 1.0 mL/min. The detection wavelength was set at 205 nm, and the injection volume was 10 µL. The results demonstrated that the four NLAAs exhibited good linearity in the range of 2.0-800.0 mg/L, with correlation coefficients (r)≥0.9995. The limits of detection (LODs) ranged from 0.17 to 0.49 mg/L, and limits of quantification (LOQs) ranged from 0.57 to 1.63 mg/L. The relative standard deviations (RSDs) for precision, repeatability, and stability over 24 h were all below 2.0%. Using this method, the NLAA contents of five facial-cleanser products were determined. The results demonstrated that all five samples contained one or more NLAAs, and the total NLAA contents ranged from 64.58 to 97.01 mg/g. The five spiked-sample recoveries of the NLAAs at four different spiked levels (0.60, 4.50, 15.00, 24.00 mg/g) ranged from 94.3% to 107.4%, indicating satisfactory accuracy. However, the actual NLAA composition and label for one facial-cleanser product were not consistent with our test results. This finding demonstrates the necessity of strengthening market monitoring through testing. The proposed method has the advantages of simple pretreatment, rapid testing, good precision, high accuracy, and appropriate stability. Thus, it is suitable for the determination of NLAA contents in facial cleansers and provides an effective technical reference for the raw-material purity assessment, synthetic yield detection, and product quality control of this type of surfactant.

Influence of watershed characteristics and human activities on the occurrence of organophosphate esters related to dissolved organic matter in estuarine surface water.

Organophosphate esters (OPEs) are widespread in aquatic environments and pose potential threats to ecosystem and human health. Here, we profiled OPEs in surface water samples of heavily urbanized estuaries in eastern China and investigated the influence of watershed characteristics and human activities on the spatial distribution of OPEs related to dissolved organic matter (DOM). The total OPE concentration ranged from 22.3 to 1201 ng/L, with a mean of 162.6 ± 179.8 ng/L. Chlorinated OPEs were the predominant contaminant group, accounting for 27.4-99.6 % of the total OPE concentration. Tris(2-chloroisopropyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, and tributyl phosphate were the dominant compounds, with mean concentrations of 111.2 ± 176.0 ng/L, 22.6 ± 21.5 ng/L, and 14.8 ± 14.9 ng/L, respectively. Variable OPE levels were observed in various functional areas, with significantly higher concentrations in industrial areas than in other areas. Potential source analysis revealed that sewage treatment plant effluents and industrial activities were the primary OPE sources. The total OPE concentrations were negatively correlated to the mean slope, plan curvature, and elevation, indicating that watershed characteristics play a role in the occurrence of OPEs. Individual OPEs (triisobutyl phosphate, tris(2-butoxyethyl) phosphate, tris(2-chloroethyl) phosphate, and tricresyl phosphate) and Σalkyl-OPEs were positively correlated to the night light index or population density, suggesting a significant contribution of human activity to OPE pollution. The co-occurrence of OPEs and DOM was also observed, and the fluorescence indices of DOM were found to be possible indicators for tracing OPEs. These findings can elucidate the potential OPE dynamics in response to DOM in urbanized estuarine water environments with intensive human activities.

Evaluation of the DGT passive samplers for integrating fluctuating concentrations of pharmaceuticals in surface water.

Diffusive gradients in thin films (DGTs) have been well-documented for the measurement of a broad range of organic pollutants in surface water. However, the performance has been challenged by the inherent periodic concentration fluctuations for most organic pollutants. Therefore, there is an urgent need to assess the true time-weighted average (TWA) concentration based on fluctuating concentration profiles. The study aimed to evaluate the responsiveness of DGT and accuracy of TWA concentrations, considering various concentration fluctuating scenarios of 20 pharmaceuticals in surface water. The reliability and accuracy of the TWA concentrations measured by the DGT were assessed by comparison with the sum of cumulative mass of DGT exposed at different stages over the deployment period. The results showed that peak concentration duration (1-5 days), peak concentration fluctuation intensity (6-20 times), and occurrence time of peak concentration fluctuation (early, middle, and late stages) have minimal effect on DGT's response to most target pharmaceutical concentration fluctuations (0.8 < CDGT/CTWA < 1.2). While the downward-bent accumulations of a few pharmaceuticals on DGT occur as the sampling time increases, which could be accounted for by capacity effects during a long-time sampling period. Additionally, the DGT device had good sampling performance in recording short fluctuating concentrations from a pulse event returning to background concentrations with variable intensity and duration. This study revealed a satisfactory capacity for the evaluation of the TWA concentration of pharmaceuticals integrated over the period of different pulse deployment for DGT, suggesting that this passive sampler is ideally suited as a monitoring tool for field application. This study represents the first trial for evaluating DGT sampling performance for pharmaceuticals with multiple concentration fluctuating scenarios over time, which would be valuable for assessing the pollution status in future monitoring campaign.

A landscape source-sink model to understanding the seasonal dynamics of antibiotics in soils at watershed scale.

Human and veterinary antibiotics occur widely in soil ecosystems and pose a serious threat to soil health. Landscape structure can be linked to Earth surface processes and anthropogenic footprints and may influence the variability of antibiotics in soil. In this study, an improved landscape source-sink model was used to characterize source-sink structures using the location-weighted landscape index (LWLI), which can be linked to antibiotic seasonality. The topographic wetness index was employed to identify source and sink landscapes, which represent antibiotic transport pathways via topography-driven hydrological processes. The results indicate that LWLI values and antibiotic seasonality are typically higher in farmland soils than in forest and orchard soils. LWLI values exhibit significant positive correlations with antibiotic seasonality in soils (R2: 0.33-0.58). Furthermore, landscape source-sink structures have a significant influence on antibiotic seasonality between winter and other seasons in farmland soils; however, these structures affect antibiotic seasonality between summer and other seasons in forest and orchard soils. The results of this study indicate that water movement regulated by landscape structure may play a crucial role in influencing antibiotic seasonality in soils at the watershed scale, and the landscape source-sink model can be used to quantitatively evaluate antibiotic seasonality in soil environment.

Occurrence, Source Apportionment, and Ecological Risk of Typical Pharmaceuticals in Surface Waters of Beijing, China.

Various studies have shown that the heavy use of pharmaceuticals poses serious ecological risks, especially in metropolitan areas with intensive human activities. In this study, the spatial distribution, sources, and ecological risks of 29 pharmaceuticals in 82 surface waters collected from the North Canal Basin in Beijing were studied. The results showed that the pharmaceutical concentrations ranged from not detected to 193 ng/L, with ampicillin being undetected while ofloxacin had a 100% detection frequency, which indicates the widespread occurrence of pharmaceutical pollution in the North Canal Basin. In comparison with other freshwater study areas, concentrations of pharmaceuticals in the North Canal Basin were generally at moderate levels. It was found that pharmaceutical concentrations were always higher in rivers that directly received wastewater effluents. Source analysis was conducted using the positive matrix factorization model. Combining the spatial pollution patterns of pharmaceuticals, it has been found that wastewater effluents contributed the most to the loads of pharmaceuticals in the studied basin, while in suburban areas, a possible contribution of untreated wastewater was demonstrated. Risk assessment indicated that approximately 55% of the pharmaceuticals posed low-to-high ecological risks, and combining the results of risk analyses, it is advised that controlling WWTP effluent is probably the most cost-effective measure in treating pharmaceutical pollution.

Emerging Contaminants in the Effluent of Wastewater Should Be Regulated: Which and to What Extent?

Effluent discharged from urban wastewater treatment plants (WWTPs) is a major source of emerging contaminants (ECs) requiring effective regulation. To this end, we collected discharge datasets of pharmaceuticals (PHACs) and endocrine-disrupting chemicals (EDCs), representing two primary categories of ECs, from Chinese WWTP effluent from 2012 to 2022 to establish an exposure database. Moreover, high-risk ECs' long-term water quality criteria (LWQC) were derived using the species sensitivity distribution (SSD) method. A total of 140 ECs (124 PHACs and 16 EDCs) were identified, with concentrations ranging from N.D. (not detected) to 706 µg/L. Most data were concentrated in coastal regions and Gansu, with high ecological risk observed in Gansu, Hebei, Shandong, Guangdong, and Hong Kong. Using the assessment factor (AF) method, 18 high-risk ECs requiring regulation were identified. However, only three of them, namely carbamazepine, ibuprofen, and bisphenol-A, met the derivation requirements of the SSD method. The LWQC for these three ECs were determined as 96.4, 1010, and 288 ng/L, respectively. Exposure data for carbamazepine and bisphenol-A surpassed their derived LWQC, indicating a need for heightened attention to these contaminants. This study elucidates the occurrence and risks of ECs in Chinese WWTPs and provides theoretical and data foundations for EC management in urban sewage facilities.

Urbanization and land use regulate soil vulnerability to antibiotic contamination in urban green spaces.

The presence of antibiotics in environment is an emerging concern because of their ubiquitous occurrence, adverse eco-toxicological effects, and promotion of widespread antibiotic resistance. Urban soil, which plays a noticeable role in human health, may be a reservoir of antibiotics because of intensive human disturbance. However, little is understood about the vulnerability of soil to antibiotic contamination in urban areas and the spatial-temporal characteristics of anthropogenic and environmental pressures. In this study, we developed a framework for the dynamic assessment of soil vulnerability to antibiotic contamination in urban green spaces, combining antibiotic release, exposure, and consequence layers. According to the results, soil vulnerability risks shown obvious spatial-temporal variation in urban areas. Areas at a high risk of antibiotic contamination were usually found in urban centers with high population densities and in seasons with low temperature and vegetation coverage. Quinolones (e.g., ofloxacin and norfloxacin) were priority antibiotics that posed the highest vulnerability risks, followed by tetracyclines. We also confirmed the effectiveness of the vulnerability assessment by correlating soil vulnerability indexes and antibiotic residues in urban soils. Furthermore, urbanization- and land use-related parameters were shown to be critical in regulating soil vulnerability to antibiotic contamination based on sensitivity analysis. These findings have important implications for the prediction and mitigation of urban soil contamination with antibiotics and strategies to improve human health.