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18 pages, 6409 KiB  
Communication
A Highly Stable Electrochemical Sensor Based on a Metal–Organic Framework/Reduced Graphene Oxide Composite for Monitoring the Ammonium in Sweat
by Yunzhi Hua, Junhao Mai, Rourou Su, Chengwei Ma, Jiayi Liu, Cong Zhao, Qian Zhang, Changrui Liao and Yiping Wang
Biosensors 2024, 14(12), 617; https://doi.org/10.3390/bios14120617 (registering DOI) - 15 Dec 2024
Abstract
The demand for non-invasive, real-time health monitoring has driven advancements in wearable sensors for tracking biomarkers in sweat. Ammonium ions (NH4+) in sweat serve as indicators of metabolic function, muscle fatigue, and kidney health. Although current ion-selective all-solid-state printed sensors [...] Read more.
The demand for non-invasive, real-time health monitoring has driven advancements in wearable sensors for tracking biomarkers in sweat. Ammonium ions (NH4+) in sweat serve as indicators of metabolic function, muscle fatigue, and kidney health. Although current ion-selective all-solid-state printed sensors based on nanocomposites typically exhibit good sensitivity (~50 mV/log [NH4+]), low detection limits (LOD ranging from 10−6 to 10−7 M), and wide linearity ranges (from 10−5 to 10−1 M), few have reported the stability test results necessary for their integration into commercial products for future practical applications. This study presents a highly stable, wearable electrochemical sensor based on a composite of metal–organic frameworks (MOFs) and reduced graphene oxide (rGO) for monitoring NH4+ in sweat. The synergistic properties of Ni-based MOFs and rGO enhance the sensor’s electrochemical performance by improving charge transfer rates and expanding the electroactive surface area. The MOF/rGO sensor demonstrates high sensitivity, with a Nernstian response of 59.2 ± 1.5 mV/log [NH4+], an LOD of 10−6.37 M, and a linearity range of 10−6 to 10−1 M. Additionally, the hydrophobic nature of the MOF/rGO composite prevents water layer formation at the sensing interface, thereby enhancing long-term stability, while its high double-layer capacitance minimizes potential drift (7.2 µV/s (i = ±1 nA)) in short-term measurements. Extensive testing verified the sensor’s exceptional stability, maintaining consistent performance and stable responses across varying NH4+ concentrations over 7 days under ambient conditions. On-body tests further confirmed the sensor’s suitability for the continuous monitoring of NH4+ levels during physical activities. Further investigations are required to fully elucidate the impact of interference from other sweat components (such as K+, Na+, Ca2+, etc.) and the influence of environmental factors (including the subject’s physical activity, posture, etc.). With a clearer understanding of these factors, the sensor has the potential to emerge as a promising tool for wearable health monitoring applications. Full article
(This article belongs to the Special Issue Advanced Electrochemical Biosensors and Their Applications)
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Figure 1
<p>The synthesis of Ni-MOF/rGO composite and deposition on working electrode (WE).</p>
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<p>Schematic fabrication process of the all-solid-state MOF/rGO-modified wearable sweat sensor.</p>
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<p>SEM micrographs of MOF/rGO composite structure at different MOF to rGO ratios (M:G).</p>
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<p>(<b>a</b>) SEM micrograph of the MOF/rGO composite (MOF/rGO ratio = 10:1); (<b>b</b>) zoomed-in SEM micrograph of the same MOF/rGO composite (All scale bars = 1 μm).</p>
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<p>X-ray diffraction (XRD) patterns of rGO, MOF, and MOF/rGO composite.</p>
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<p>Raman spectra of GO, rGO, MOF, and MOF/rGO composite.</p>
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<p>FTIR spectra of rGO, MOF, and rGO/MOF composite.</p>
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<p>Nyquist plots of (<b>a</b>) bare WE, MOF-modified WE, and MOF/rGO-modified WE in 0.1 M NH<sub>4</sub>Cl solution (AC amplitude: 100 mV; frequency range: 0.1 Hz to 1 MHz); (<b>b</b>) magnified view of the Nyquist plot for the MOF/rGO-modified WE (MOF/rGO ratio of 10:1); (<b>c</b>) Nyquist plots of MOF/rGO-modified electrodes with various M:G ratios.</p>
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<p>CV results at different scan rates for (<b>a</b>) MOF, (<b>b</b>) rGO, and (<b>c</b>) MOF/rGO-modified electrodes, and plots of anodic peak currents versus the square root of the scan rate for (<b>d</b>) MOF, (<b>e</b>) rGO, and (<b>f</b>) MOF/rGO.</p>
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<p>CV test results of the bare carbon electrode, MOF, rGO, and MOF/rGO-modified electrodes at a scan rate of 100 mV/s.</p>
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<p>(<b>a</b>) Potential response of the sweat sensor to varying NH<sub>4</sub><sup>+</sup> concentrations over time (NH<sub>4</sub>Cl from 10<sup>−8</sup> to 10<sup>−1</sup> M); (<b>b</b>) reversibility test of the potential response (NH<sub>4</sub>Cl from 10<sup>−5</sup> to 10<sup>−1</sup> M).</p>
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<p>Chronopotentiometry test results of sensors with configurations of CE+NH<sub>4</sub><sup>+</sup> ISM, CE+MOF+NH<sub>4</sub><sup>+</sup> ISM, CE+rGO+NH<sub>4</sub><sup>+</sup> ISM, and CE+MOF/rGO+NH<sub>4</sub><sup>+</sup> ISM under currents of (<b>a</b>) ±1 nA and (<b>b</b>) ±10 nA.</p>
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<p>Aqueous layer test results for sensors with bare carbon ISM and MOF/rGO ISM in 0.1 M NH<sub>4</sub>Cl and 0.1 M NaCl solutions.</p>
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<p>Contact angle test results of (<b>a</b>) screen-printed bare carbon WE, (<b>b</b>) rGO-CNT-modified WE, and (<b>c</b>) MOF/rGO-modified WE.</p>
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<p>(<b>a</b>) Long-term stability of MOF/rGO-based sensors in NH<sub>4</sub>Cl solutions with electrolyte concentrations ranging from 10<sup>−8</sup> to 10<sup>−1</sup> M; (<b>b</b>) sensitivity change over time for sensors with bare carbon electrodes and MOF/rGO-modified electrodes.</p>
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<p>(<b>a</b>) On-body testing of the MOF/rGO-based sweat sensor placed on the participant’s forehead during exercise; (<b>b</b>) close-up view of the wearable MOF/rGO-modified sweat sensor; (<b>c</b>) and (<b>d</b>) real-time measurement of ammonium levels in sweat, showing the onset of perspiration and the subsequent stabilization of potential.</p>
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13 pages, 4035 KiB  
Communication
Use of Laccase Enzymes as Bio-Receptors for the Organic Dye Methylene Blue in a Surface Plasmon Resonance Biosensor
by Araceli Sánchez-Álvarez, Gabriela Elizabeth Quintanilla-Villanueva, Osvaldo Rodríguez-Quiroz, Melissa Marlene Rodríguez-Delgado, Juan Francisco Villarreal-Chiu, Analía Sicardi-Segade and Donato Luna-Moreno
Sensors 2024, 24(24), 8008; https://doi.org/10.3390/s24248008 (registering DOI) - 15 Dec 2024
Viewed by 108
Abstract
Methylene blue is a cationic organic dye commonly found in wastewater, groundwater, and surface water due to industrial discharge into the environment. This emerging pollutant is notably persistent and can pose risks to both human health and the environment. In this study, we [...] Read more.
Methylene blue is a cationic organic dye commonly found in wastewater, groundwater, and surface water due to industrial discharge into the environment. This emerging pollutant is notably persistent and can pose risks to both human health and the environment. In this study, we developed a Surface Plasmon Resonance Biosensor employing a BK7 prism coated with 3 nm chromium and 50 nm of gold in the Kretschmann configuration, specifically for the detection of methylene blue. For the first time, laccases immobilized on a gold surface were utilized as bio-receptors for this organic dye. The enzyme was immobilized using carbodiimide bonds with EDC/NHS crosslinkers, allowing for the analysis of samples with minimal preparation. The method demonstrated validation with a limit of detection (LOD) of 4.61 mg L−1 and a limit of quantification (LOQ) of 15.37 mg L−1, a working range of 0–100 mg L−1, and an R2 value of 0.9614 during real-time analysis. A rainwater sample spiked with methylene blue yielded a recovery rate of 122.46 ± 4.41%. The biosensor maintained a stable signal over 17 cycles and remained effective for 30 days at room temperature. Full article
(This article belongs to the Section Biosensors)
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Figure 1
<p>Chemical structure of methylene blue.</p>
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<p>Possible recognition process and first step of degradation of methylene blue by laccases.</p>
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<p>Immobilization process of laccases on the thin chromium–gold film chip. In the step 1, alkanethiols are added to the thin gold surface. In step 2, the EDC is added, forming an unstable intermediate. In step 3, the NHS is added, creating a sulfo-NHS ester. In step 4, NHS is replaced by the laccase through an amide bond.</p>
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<p>Assembly of the prism and the chip on the SPR equipment: (<b>a</b>) assembly of the prism, the chip with a thin gold film with the immobilized laccases, the prism and other components. (<b>b</b>) Set up of the prism, sample cell, chip with immobilized laccases and the other on the SPR equipment.</p>
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<p>Reflectance spectra obtained by angular sweep.</p>
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<p>Immobilization process of laccass from <span class="html-italic">Rhus vernicifera</span> in real-time by SPR.</p>
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<p>FTIR analysis of different stages of laccase immobilization.</p>
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<p>(<b>a</b>) SPR analysis of stocks with different concentrations of methylene blue. (<b>b</b>) Calibration curve and equation of a straight line.</p>
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<p>Comparison of the intensity of reflectance of solutions of methylene blue at day 1 and day 30.</p>
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16 pages, 1184 KiB  
Article
Organic Fertilizers as Partial Substitutes for Chemical Fertilizers Enhance Nitrogen Immobilization and Optimize Nitrogen Fate in Paddy Soils
by Hongqian Hou, Jianhua Ji, Xianjin Lan, Marios Drosos, Xiumei Liu, Zhenzhen Lv, Yiren Liu, Zhengxin Cheng and Weijun Zhou
Agriculture 2024, 14(12), 2300; https://doi.org/10.3390/agriculture14122300 (registering DOI) - 14 Dec 2024
Viewed by 483
Abstract
Organic fertilizers as partial substitutes for chemical fertilizers improve soil nitrogen (N) retention capacity. However, the relative importance of biotic and abiotic N immobilization at different levels of organic N substitution and the subsequent effects on N utilization in paddy soils are not [...] Read more.
Organic fertilizers as partial substitutes for chemical fertilizers improve soil nitrogen (N) retention capacity. However, the relative importance of biotic and abiotic N immobilization at different levels of organic N substitution and the subsequent effects on N utilization in paddy soils are not well elucidated. To address these, a combination of 15N incubation experiments and pot experiments were conducted to investigate biotic and abiotic N immobilization features and their effects on N fertilizer fate under long-term different fertilization regimes in paddy soils in China. Test soils that had received chemical fertilization (NPK), chemical N was substituted with 30%, 50%, and 70% organic N (70 F + 30 M, 50 F + 50 M, and 30 F + 70 M, respectively), and no fertilization (control) for 36 years. The results revealed that both abiotic and biotic NH4+-N immobilization were enhanced under organic N substitution soils. The highest NH4+-N abiotic and biotic N immobilization was observed under 50 F + 50 M soil, significantly increasing by 195.5% and 51.4%, respectively, compared to the NPK soil. In contrast, only abiotic NO3-N immobilization increased with rising organic substitution N proportions. N fertilizer utilization efficiency was significantly enhanced in 50 F + 50 M soil (36.7%) compared to the NPK soil (30.3%), which was primarily attributed to the enhanced N pool activity and N immobilization capacity. However, the N fertilizer residue rate was significantly higher in the 30 F + 70 M soil (23.6%) compared to the NPK soil (21.6%), largely attributed to the soil properties improvement. Our results suggest that N immobilization capacity and N fertilizer utilization can be optimized with a 50% organic substitution ratio in our studied soil–crop system. Full article
(This article belongs to the Section Crop Production)
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Figure 1
<p>Immobilization of NH<sub>4</sub><sup>+</sup>-<sup>15</sup>N (<b>a</b>) and NO<sub>3</sub><sup>−</sup>-<sup>15</sup>N (<b>b</b>) in insoluble N pool by incubation time under different fertilizer treatments after a 36-year experiment. Control, no fertilization; NPK, chemical fertilization; 70 F + 30 M, 70% of chemical N plus 30% of organic N; 50 F + 50 M, 50% of chemical N plus 50% of organic N; 30 F + 70 M, 30% of chemical N plus 70% of organic N. Error bars represent standard deviations of the means (n = 3).</p>
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<p>Recovery of <sup>15</sup>N in <sup>15</sup>NH<sub>4</sub><sup>+</sup>-labeled (<b>a</b>) and <sup>15</sup>NO<sub>3</sub><sup>−</sup>-labeled (<b>b</b>) soils during 168 h incubation under different fertilization treatments after a 36-year experiment. Control, no fertilization; NPK, chemical fertilization; 70 F + 30 M, 70% of chemical N plus 30% of organic N; 50 F + 50 M, 50% of chemical N plus 50% of organic N; 30 F + 70 M, 30% of chemical N plus 70% of organic N. Error bars represent standard deviations of the means (n = 3). Different letters in the bars of the same N pool indicate significant differences among fertilizer treatments at the <span class="html-italic">p</span> ≤ 0.05 level (Duncan’s test).</p>
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<p>Immobilization of NH<sub>4</sub><sup>+</sup>-N (<b>a</b>), NO<sub>3</sub><sup>−</sup>-N (<b>b</b>), and abiotic/biotic ratio (<b>c</b>) under different fertilization treatments after a 36-year experiment. Control, no fertilization; NPK, chemical fertilization; 70 F + 30 M, 70% of chemical N plus 30% of organic N; 50 F + 50 M, 50% of chemical N plus 50% of organic N; 30 F + 70 M, 30% of chemical N plus 70% of organic N. Abiotic/biotic, soil abiotic N immobilization divided by biotic N immobilization. Error bars represent standard deviations of the means (n = 3). Different letters in the bars of the same variable indicate significant differences among fertilizer treatments at the <span class="html-italic">p</span> ≤ 0.05 level (Duncan’s test).</p>
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<p>Structural equation modeling (SEM) analysis of the relationship between different soil properties, N pool activity, N immobilization, N fertilizer uptake, and residue. Indicators in the box specify observed or potential variables, respectively. Soil properties include soil organic matter (SOM) and microbial biomass nitrogen (MBN); N pool activity includes acid-hydrolyzable ammonium N (AHAN) and amino acid N (AAN); N immobilization includes biotic immobilization of NH<sub>4</sub><sup>+</sup>-N (Biotic-a) and abiotic immobilization of NO<sub>3</sub><sup>−</sup>-N (Abiotic-n). R<sup>2</sup> indicates the explanatory power of the variables. The path coefficients with significant effects are designated by solid red lines, and the thickness of the lines indicates significance. “*” and “***” specify <span class="html-italic">p</span> &lt; 0.05 and <span class="html-italic">p</span> &lt; 0.001, and path coefficients with no significant difference are indicated by dashed blue lines.</p>
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17 pages, 6264 KiB  
Article
Linking Water Quality Indicators in Stable Reservoir Ecosystems: Correlation Analysis and Ecohydrological Implications
by Juan Du, Xiao Yang, Peng Xu, Xiang Wan, Pan Wang, Ding Wang, Qi Yang, Qiu Wang and Amar Razzaq
Water 2024, 16(24), 3600; https://doi.org/10.3390/w16243600 (registering DOI) - 14 Dec 2024
Viewed by 334
Abstract
This research was conducted to determine the connections between dissolved oxygen (DO), chemical oxygen demand (COD), permanganate index (CODMn), five-day biochemical oxygen demand (BOD5), and ammonia nitrogen (NH3-H) across five reservoirs of Yunmeng County, China, from January to November [...] Read more.
This research was conducted to determine the connections between dissolved oxygen (DO), chemical oxygen demand (COD), permanganate index (CODMn), five-day biochemical oxygen demand (BOD5), and ammonia nitrogen (NH3-H) across five reservoirs of Yunmeng County, China, from January to November 2022. Each month, water samples were collected and subjected to analysis using standard methods. The samples were collected and analyzed using standard methods: dissolved oxygen was determined using the electrochemical probe method, COD was measured via the rapid digestion spectrophotometric method, CODMn was detected using the potassium permanganate oxidation method, BOD5 was determined using the dilution and inoculation method, and NH3-N was measured by using the Nessler reagent spectrophotometry method. The results confirmed strong positive correlations between COD and CODMn, with different intensities from reservoir to reservoir. More specific and demanding COD parameters were used to estimate the level of oxygen consumption; hence, a more variable correlation strength was observed between BOD5 and the other two parameters. Thus, BOD5 was found to be the main indicator of biodegradable organic matter and bacterial oxygen consumption. However, the results were negative, showing a decreasing trend. This means that the oxygen content was lower in the majority of reservoirs, which is attributed to the decomposition of ammonia nitrogen and the presence of organic matter. These findings significantly contribute to the development of appropriate programs for efficient water quality monitoring and the development of reservoir-specific management strategies. This study suggests that there is a need for continuous monitoring of these parameters, together with the extension of the program to additional reservoirs and water quality indicators, along with the use of advanced modeling techniques to clarify the underlying factors that connect water quality parameters in these complex reservoir ecosystems. Full article
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<p>Sampling sites map of surface water of selected reservoirs. Satellite Imagery Source: Esri, ArcGIS Imagery.</p>
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<p>Correlation analysis of COD<sub>Mn</sub> and COD.</p>
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<p>Correlation analysis of COD<sub>Mn</sub> and COD.</p>
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<p>Correlation analysis of COD<sub>Mn</sub> and BOD<sub>5</sub>.</p>
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<p>Correlation analysis of COD<sub>Mn</sub> and BOD<sub>5</sub>.</p>
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<p>Correlation analysis of BOD<sub>5</sub> and COD.</p>
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<p>The relationship between the BOD<sub>5</sub> concentration change and index ratio among the five reservoirs.</p>
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<p>Result statistics chart of DO, COD, COD<sub>Mn</sub>, BOD<sub>5</sub>, and NH<sub>3</sub>-H among the five reservoirs.</p>
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<p>Result statistics chart of DO, COD, COD<sub>Mn</sub>, BOD<sub>5</sub>, and NH<sub>3</sub>-H among the five reservoirs.</p>
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<p>Result statistics chart of water temperature, transparency, chlorophyll-a, and turbidity in the five reservoirs.</p>
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<p>Result statistics chart of water temperature, transparency, chlorophyll-a, and turbidity in the five reservoirs.</p>
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<p>Result statistics chart of water temperature, transparency, chlorophyll-a, and turbidity in the five reservoirs.</p>
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18 pages, 20230 KiB  
Article
Understanding Emission Trends, Regional Distribution Differences, and Synergistic Emission Effects in the Transportation Sector in Terms of Social Factors and Energy Consumption
by Yu Zhao and Prasanna Divigalpitiya
Sustainability 2024, 16(24), 10971; https://doi.org/10.3390/su162410971 (registering DOI) - 13 Dec 2024
Viewed by 304
Abstract
China’s transportation sector plays a significant role in reducing carbon dioxide (CO2) and air pollution. Previous studies have predominantly utilized scenario analysis to forecast emissions for the next 30 to 50 years based on coefficients from a base year. To elucidate [...] Read more.
China’s transportation sector plays a significant role in reducing carbon dioxide (CO2) and air pollution. Previous studies have predominantly utilized scenario analysis to forecast emissions for the next 30 to 50 years based on coefficients from a base year. To elucidate the current state of gas emissions in the transportation sector, this study employed panel data for 10 types of gas emissions from 2001 to 2020, analyzing their emission characteristics, tendencies, and synergistic effects. Utilizing the Kaya equation and the logarithmic mean division index (LMDI) decomposition method, we developed a model of pollutant emissions that considers the synergistic effects, pollution emission intensity, energy mix, energy consumption intensity, and population. The results show that all pollutants in the transportation sector decreased except for NH3 and CO2. There was a synergistic effect between air pollutants and CO2 emissions, but the reduction was not significant. From 2013 to 2020, the transportation sector shifted from a high emission intensity with low synergy to a low emission intensity with high synergy. The results indicate that off-road mobile vehicles, on-road diesel vehicles, and motorcycles became the main source of emissions from transportation in certain provinces, and a key area requiring attention in policy development. Gasoline consumption was identified as the primary contributor to the significant increase in synergistic emission variability in the transportation sector. These results provide policymakers with practical ways to optimize emission reduction pathways. Full article
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<p>Analysis structure. Note: this study analyzed 10 types of emissions from four pollution sources. On the left side is the sequence of research steps, while the corresponding research methods are presented on the right side (source: created by the authors).</p>
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<p>Sources of pollutant emissions in 2020.</p>
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<p>Sources of pollutants and changes in emissions. Note: The subfigures (<b>a</b>–<b>j</b>) show sources of CO<sub>2</sub>, CO, PM<sub>2.5</sub>, PM<sub>10</sub>, BC, OC, VOC, NOx, SO<sub>2</sub>, NH<sub>3</sub>, separately.</p>
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<p>Changes relative to the previous year.</p>
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<p>Emission intensity and synergistic effects in 2013 and 2020. Note: The subfigures (<b>a</b>–<b>f</b>) show synergistic effect of the pollutant with CO<sub>2</sub>. The red dots mark the average of the 30 provinces and cities.</p>
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<p>Variations in emission origins across four provinces and cities. Note: The subfigures (<b>a</b>–<b>f</b>) show sources of PM<sub>2.5</sub>, PM<sub>10</sub>, NOx, VOC, SO<sub>2</sub>, CO<sub>2</sub>, separately.</p>
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<p>Theil index with population and gasoline as the base.</p>
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<p>Province categories.</p>
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<p>Emission origins of the seven major regions.</p>
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15 pages, 3448 KiB  
Article
Impact of Biochar Addition on Biofloc Nitrifying Bacteria and Inorganic Nitrogen Dynamics in an Intensive Aquaculture System of Shrimp
by Wujie Xu, Demin Zhang, Haochang Su, Yu Xu, Xiaojuan Hu, Guoliang Wen and Yucheng Cao
Microorganisms 2024, 12(12), 2581; https://doi.org/10.3390/microorganisms12122581 - 13 Dec 2024
Viewed by 240
Abstract
In this study, an eight-week culture trial of Penaeus vannamei juveniles was conducted in commercial intensive systems to compare the impacts of biochar and molasses addition on biofloc nitrifying bacteria and inorganic nitrogen dynamics under limited water exchange conditions. During the trial, the [...] Read more.
In this study, an eight-week culture trial of Penaeus vannamei juveniles was conducted in commercial intensive systems to compare the impacts of biochar and molasses addition on biofloc nitrifying bacteria and inorganic nitrogen dynamics under limited water exchange conditions. During the trial, the biofloc concentration (in terms of VSS and TSS), quantities of total bacteria (TB) and total Vibrio (TV), and ratio of TV/TB in the culture water were lower in the biochar group compared to the molasses group. Metagenomic sequencing analysis revealed that the bacterial community composition of bioflocs showed higher α-diversity and complexity in the biochar group compared to the molasses group. Moreover, the abundance of nitrifying bacterial genera and functional genes in bioflocs was higher in the biochar group compared to the molasses group. Inorganic nitrogen dynamics showed that NH4+-N and NO2-N were better controlled in the biochar group compared to the molasses group, as reflected by lower peaks of NH4+-N and NO2-N and higher NO3-N concentrations. Excellent production performance of shrimp was achieved, which in turn proved the reliable effect of biochar addition on the mediation of inorganic nitrogen transformation through nitrifying bacteria. These results showed that biochar addition could promote biofloc nitrifying bacteria and nitrification to more effectively control harmful nitrogen for shrimp efficient production. This study provides a practical example for the biochar application in biofloc-based systems for intensive aquaculture. Full article
(This article belongs to the Special Issue Aquatic Microorganisms and Their Application in Aquaculture)
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<p>Change in biofloc concentration in the culture water of biofloc systems with the addition of biochar and molasses in an 8-week culture trial of shrimp (means ± S.D., <span class="html-italic">n</span> = 6). (<b>A</b>): VSS—volatile suspended solids; (<b>B</b>): TSS—total suspended solids. The asterisk (*) indicates a significant difference between the two groups (* <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01).</p>
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<p>Quantity changes in total bacteria and total <span class="html-italic">Vibrio</span> in the culture water of biofloc systems with the addition of biochar and molasses in an 8-week culture trial of shrimp (means ± S.D., <span class="html-italic">n</span> = 6). (<b>A</b>): Total bacteria; (<b>B</b>): total <span class="html-italic">Vibrio</span>; (<b>C</b>): ratio of total <span class="html-italic">Vibrio</span>/total bacteria. The asterisk (*) indicates a significant difference between the two groups (* <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01).</p>
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<p>Inorganic nitrogen dynamics in the culture water of biofloc systems with the addition of biochar and molasses in an 8-week culture trial of shrimp (means ± S.D., <span class="html-italic">n</span> = 6). (<b>A</b>): NH<sub>4</sub><sup>+</sup>-N; (<b>B</b>): NO<sub>2</sub><sup>−</sup>-N; (<b>C</b>): NO<sub>3</sub><sup>−</sup>-N. The asterisk (*) indicates a significant difference between the two groups (* <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01).</p>
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<p>Diversity and composition of bacterial communities in the bioflocs with the addition of biochar and molasses in an 8-week culture trial of shrimp (means ± S.D., <span class="html-italic">n</span> = 6). (<b>A</b>): Bacterial alpha diversity; (<b>B</b>): bacterial composition at phylum level; (<b>C</b>): bacterial beta diversity. The asterisk (*) indicates a significant difference between the two groups (* <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01).</p>
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<p>Correlation networks of dominant bacterial genera and N-cycling genes in the bioflocs with the addition of biochar and molasses in an 8-week culture trial of shrimp (means ± S.D., <span class="html-italic">n</span> = 6). (<b>A</b>): Network of the top 30 bacterial genera in the biochar and molasses groups; (<b>B</b>): network of top 30 N-cycling genes in the biochar and molasses groups.</p>
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<p>Inorganic N-transformation pathways and involved functional genes and bacterial genera in the bioflocs with the addition of biochar and molasses in an 8-week culture trial of shrimp (means ± S.D., <span class="html-italic">n</span> = 6). (<b>A</b>): Inorganic N-transformation pathways and genes; (<b>B</b>): nitrifying functional genes; (<b>C</b>): autotrophic nitrifying bacterial genera; (<b>D</b>): heterotrophic nitrifying bacterial genera. The asterisk (*) indicates a significant difference between the two groups (* <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01).</p>
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11 pages, 7357 KiB  
Article
Valence State and Catalytic Activity of Ni-Fe Oxide Embedded in Carbon Nanotube Catalysts
by Jaekwang Lee and Heesoo Lee
Nanomaterials 2024, 14(24), 2004; https://doi.org/10.3390/nano14242004 - 13 Dec 2024
Viewed by 260
Abstract
The catalytic activity of Ni-Fe oxide embedded in CNTs was investigated in terms of valence states and active oxygen species. Ni-Fe oxides were prepared by the sol-gel combustion process, and Ni-Fe oxides embedded in CNT catalysts were synthesized by the catalytic chemical vapor [...] Read more.
The catalytic activity of Ni-Fe oxide embedded in CNTs was investigated in terms of valence states and active oxygen species. Ni-Fe oxides were prepared by the sol-gel combustion process, and Ni-Fe oxides embedded in CNT catalysts were synthesized by the catalytic chemical vapor deposition (CCVD) method. The lattice structure of the Ni-Fe oxide catalysts was analyzed, and the lattice distortion was increased with the addition of Fe. The specific surface areas and pore structures of the Ni-Fe oxides embedded in CNTs were determined through the BET method. The nano-sized Ni-Fe oxides embedded in CNTs were observed using morphology analysis. The crystallinity and defects of CNTs were analyzed by Raman spectroscopy, and the ID/IG ratio of Ni1.25Fe0.75O/CNT was the lowest at 0.36, representing the high graphitization and low structural defects of the CNT surface. The valence states of Fe and Ni were changed by the interaction between catalysts and CNTs. The redox property of the catalysts was evaluated by H2-TPR analysis, and the H2 consumption of Ni1.25Fe0.75O/CNT was the highest at 2.764 mmol/g. The catalytic activity of Ni-Fe oxide embedded in CNT exhibited much higher activity than Ni-Fe oxide for the selective catalytic reduction of NOx with NH3 in the temperature range of 100 °C to 450 °C. Full article
(This article belongs to the Section Energy and Catalysis)
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<p>X-ray diffraction pattern analysis of Ni-Fe oxide/CNT (<b>a</b>) and with the magnifications of the NiO (2 2 2) plane region (<b>b</b>).</p>
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<p>N<sub>2</sub> adsorption–desorption isotherms (<b>a</b>) and pore distribution (<b>b</b>) of Ni-Fe oxide/CNT.</p>
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<p>TEM images and EDS mapping of Ni<sub>0.75</sub>Fe<sub>1.25</sub>O/CNT (<b>a</b>), Ni<sub>1.0</sub>Fe<sub>1.0</sub>O/CNT (<b>b</b>), Ni<sub>1.25</sub>Fe<sub>0.75</sub>O/CNT (<b>c</b>), and Ni<sub>1.50</sub>Fe<sub>0.50</sub>O/CNT (<b>d</b>).</p>
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<p>Raman spectra of Ni-Fe oxide/CNT.</p>
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<p>XPS spectra of Fe 2p, Ni 2p, and O 1s for Ni<sub>0.75</sub>Fe<sub>1.25</sub>O/CNT (<b>a</b>), Ni<sub>1.0</sub>Fe<sub>1.0</sub>O/CNT (<b>b</b>), Ni<sub>1.25</sub>Fe<sub>0.75</sub>O/CNT (<b>c</b>), Ni<sub>1.50</sub>Fe<sub>0.50</sub>O/CNT (<b>d</b>), and Ni<sub>1.25</sub>Fe<sub>0.75</sub>O (<b>e</b>).</p>
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<p>H<sub>2</sub>-TPR profiles of the Ni-Fe oxide/CNT.</p>
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<p>Comparison of NOx conversion efficiency of Ni-Fe oxide in embedded CNT and Ni-Fe oxide. Reaction conditions: [NO] = 1000 ppm or [NH<sub>3</sub>] = 1000 ppm, [O<sub>2</sub>] = 5 vol%, N<sub>2</sub> balance and GHSV = 5000 h<sup>−1</sup>.</p>
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18 pages, 6924 KiB  
Article
Production and Optimization of Biosurfactant Properties Using Candida mogii and Licuri Oil (Syagrus coronata)
by Peterson F. F. da Silva, Renata R. da Silva, Leonie A. Sarubbo and Jenyffer M. C. Guerra
Foods 2024, 13(24), 4029; https://doi.org/10.3390/foods13244029 - 13 Dec 2024
Viewed by 570
Abstract
Optimizing biosurfactant (BS) production is key for sustainable industrial applications. This study investigated BS synthesis by Candida mogii using licuri oil, a renewable carbon source rich in medium-chain fatty acids. Process optimization was conducted via central composite design (CCD), adjusting concentrations of licuri [...] Read more.
Optimizing biosurfactant (BS) production is key for sustainable industrial applications. This study investigated BS synthesis by Candida mogii using licuri oil, a renewable carbon source rich in medium-chain fatty acids. Process optimization was conducted via central composite design (CCD), adjusting concentrations of licuri oil, glucose, NH4NO3, and yeast extract. The predictive model achieved an R2 of 0.9451 and adjusted R2 of 0.8812. Under optimized conditions, C. mogii lowered water surface tension from 71.04 mN·m−1 to 28.66 mN·m−1, with a critical micelle concentration (CMC) of 0.8 g·L−1. The biosurfactant displayed high emulsification indices, exceeding 70% for canola, licuri, and motor oils, suggesting strong potential as an industrial emulsifier. FTIR and NMR analyses confirmed its glycolipid structure. Bioassays showed no toxicity to Lactuca sativa seeds, ensuring environmental safety, while antimicrobial tests demonstrated efficacy against Staphylococcus aureus and Escherichia coli, indicating its suitability as a biocidal agent. This work positions C. mogii BS from licuri oil as a promising alternative for bioremediation, biotechnology, and antimicrobial uses. Full article
(This article belongs to the Section Food Biotechnology)
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<p>Normal plot of residuals indicating the normal distribution of the model applied to optimize the reduction in surface tension by <span class="html-italic">C. mogii</span>.</p>
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<p>Pareto chart for STred according to the statistical analysis of the CCD carried out to evaluate the effect of independent variables’ concentration in the culture medium for the biosurfactant production.</p>
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<p>Profiles for predicted values and desirability for ST<sub>red</sub> based on the statistical analysis of the CCD adopted in this study.</p>
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<p>Response profiles for the interactions between variables: (<b>A</b>) licuri oil and glucose, (<b>B</b>) licuri oil and ammonium nitrate, (<b>C</b>) licuri oil and yeast extract, (<b>D</b>) glucose and ammonium nitrate, (<b>E</b>) glucose and yeast extract, and (<b>F</b>) ammonium nitrate and yeast extract.</p>
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<p>Temporal changes in biomass, yield and surface tension during cultivation of <span class="html-italic">C. mogii</span> in mineral medium.</p>
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<p>Critical micelle concentration of the biosurfactant from <span class="html-italic">C. mogii</span>.</p>
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<p>FT-IR spectrum of biosurfactant produced by <span class="html-italic">C. mogii</span> grown in an optimized medium containing licuri oil.</p>
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<p>NMR spectrum of biosurfactant produced by <span class="html-italic">C. mogii</span> grown in an optimized medium containing licuri oil: (<b>A</b>) <sup>1</sup>H and (<b>B</b>) <sup>13</sup>C.</p>
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15 pages, 2717 KiB  
Article
Selective Recovery of Zinc from Alkaline Batteries via a Basic Leaching Process and the Use of a Machine Learning-Based Digital Twin for Predictive Purposes
by Noelia Muñoz García, José Luis Valverde, Beatriz Delgado Cano, Michèle Heitz and Antonio Avalos Ramirez
Energies 2024, 17(24), 6292; https://doi.org/10.3390/en17246292 - 13 Dec 2024
Viewed by 252
Abstract
Recycling the metals found in spent batteries offers both environmental and economic benefits, especially when extracted and purified using environmentally friendly processes. Two basic leaching agents were tested and compared: ammonium hydroxide (NH4OH) and sodium hydroxide (NaOH). Using NH4OH [...] Read more.
Recycling the metals found in spent batteries offers both environmental and economic benefits, especially when extracted and purified using environmentally friendly processes. Two basic leaching agents were tested and compared: ammonium hydroxide (NH4OH) and sodium hydroxide (NaOH). Using NH4OH 4 M at 25 °C, 30.5 ± 0.7 wt. % of zinc (Zn) was dissolved for a solid/liquid (S/L) ratio of 1/10 (g of black mass (BM)/mL of solution); meanwhile, with NaOH 6 M at 70 °C, and an S/L ratio of 1/5 (g of BM/mL of solution), 69.9 ± 2.8 wt. % of the Zn initially present in the BM of alkaline batteries was leached. A virtual representation of the experimental data through digital twins of the alkaline leaching process of the BM was proposed. For this purpose, 90% of the experimental data were used for training a supervised learning procedure involving 600 different artificial neural networks (ANNs) and using up to 12 activation functions. The application was able to choose the most suitable ANN using an ANOVA analysis. After the training step, the network was tested by predicting the outputs of inputs that were not used in the training process, to avoid overfitting in a validating process with 10% of the data. The best model was employed for estimating the degree of leaching of different metals that can be obtained from BM, obtaining a data deviation of less than 10% for highly concentrated compounds such as Zn. Full article
(This article belongs to the Section D: Energy Storage and Application)
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<p>Block diagram of the numerical procedure followed for selecting the best ANN.</p>
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<p>Extraction efficiency of Zn from BM of alkaline batteries at (<b>a</b>) 25 °C and 60 °C using NH<sub>4</sub>OH 2 M (in orange) and NH<sub>4</sub>OH 4 M (in green) and an S/L ratio of 1/10 (g of BM/mL of solution); (<b>b</b>) 25 °C, 50 °C, and 70 °C using NaOH 1 M (in red), 3 M (in blue), and 6 M (in orange) and an S/L ratio of 1/10 (g of BM/mL of solution); and (<b>c</b>) 70 °C using NaOH 6M and an S/L ratio (g of BM/mL of solution) of 1/5 (white), 1/10 (gray), and 1/20 (black).</p>
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<p>Architecture of the ANN selected.</p>
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<p>Comparison between experimental and predicted molalities (m) of chemical species in solution (output variables) produced during the NaOH-based leaching of the BM of alkaline batteries.</p>
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16 pages, 256 KiB  
Article
A Qualitative Study of Barriers and Facilitators to the Uptake of Cardiac Rehabilitation in Octogenarians
by Charlotte Nichol, Rajiv Das, Gill Barry, Michael Kelly, Ioannis Vogiatzis and Nicola Adams
Geriatrics 2024, 9(6), 161; https://doi.org/10.3390/geriatrics9060161 - 13 Dec 2024
Viewed by 277
Abstract
Introduction: Despite an established evidence-base for cardiac rehabilitation (CR) improving functional outcomes and quality of life and reducing re-hospitalisation, there is limited research on CR for older cardiac patients, who require rehabilitation the most, as they are often very deconditioned due to aortic [...] Read more.
Introduction: Despite an established evidence-base for cardiac rehabilitation (CR) improving functional outcomes and quality of life and reducing re-hospitalisation, there is limited research on CR for older cardiac patients, who require rehabilitation the most, as they are often very deconditioned due to aortic stenosis (AS). CR uptake in the UK is limited to 52% with national variability of provision and accessibility, and it is a national priority to increase uptake to 85%. Frequently, research has excluded older populations as they are deemed to be too frail or generally not suitable for inclusion. This study aimed to explore factors that can impact the uptake of CR in octogenarians. Methods: Qualitative interviews were carried out with 20 AS patients (12 female, 8 male), from a large NHS Trust in the North East of England. Results: Four main themes were identified in the data: Perceptions and Understanding, Delivery and Accessibility, Perceived Impact of Exercise and Health and Life Changes, and Transportation. Discussion: The findings suggested that the major factors were the understanding of the nature, purpose and relevance of CR to older patients, whether CR was offered, and the role of social support. Barriers and facilitators can impact uptake based on the mode of delivery and the individual circumstances identified. Future research could explore how to develop CR programmes that overcome the barriers identified in the research, such as education, monitoring strategies, use of telehealth, and home-based elements to create an acceptable and accessible programme for octogenarians. Full article
(This article belongs to the Special Issue Physical Activity and Exercise in Older Adults)
22 pages, 3173 KiB  
Article
The Nitrogen Preference of Cactus Pear (Opuntia ficus-indica): A Sand Culture Snapshot
by Nicholas A. Niechayev, Paula N. Pereira and John C. Cushman
Plants 2024, 13(24), 3489; https://doi.org/10.3390/plants13243489 - 13 Dec 2024
Viewed by 297
Abstract
Cactus pear (Opuntia-ficus indica (L.) Mill.) is an important agricultural crassulacean acid metabolism (CAM) species used as a source of food, forage, fodder, and secondary products and as a biofuel feedstock. However, the preferred source of nitrogen for this species, whether it [...] Read more.
Cactus pear (Opuntia-ficus indica (L.) Mill.) is an important agricultural crassulacean acid metabolism (CAM) species used as a source of food, forage, fodder, and secondary products and as a biofuel feedstock. However, the preferred source of nitrogen for this species, whether it be nitrate (NO3), ammonium (NH4+), or a combination of both, is not well understood. To investigate the nitrate and ammonium preference of cactus pear, we grew cladodes in sand culture with deionized water as a control or with a cross-factorial set of nutrient solutions of 0.0, 2.5, 5.0, and 10.0 mmol of nitrate and/or ammonium for one month. We then assessed a set of physiological parameters including cladode growth, relative water content, chlorophyll, tissue acidity, soluble sugars, starch, nitrate, ammonium, glyoxylic acid, nitrate reductase activity, and nitrogen and carbon content. We found significant differences in all measured parameters except for cladode length, relative water content, and carbon content. Cladodes provided with only deionized water produced no new cladodes and showed decreased soluble sugar content, increased starch content, and increased tissue acidity. We also determined the relative steady-state transcript abundance of genes that encode enzymes involved in N metabolism and CAM. Compared with control cladodes, nutrient-supplied cladodes generally showed increased or variable steady-state mRNA expression of selected CAM-related genes and nitrogen-metabolism-related genes. Our results suggest that O. ficus-indica prefers fertilizers containing either equal concentrations nitrate and ammonium or more nitrate than ammonium. Full article
(This article belongs to the Topic Plants Nutrients, 2nd Volume)
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<p>Cladode responses to nutrient treatments. (<b>A</b>) Cladode length (cm) among treatments (<span class="html-italic">n</span> = 3). (<b>B</b>) Cladode width (cm) among treatments (<span class="html-italic">n</span> = 3). (<b>C</b>) Cladode thickness (mm) among treatments (<span class="html-italic">n</span> = 6). (<b>D</b>) Cladode number among treatments (<span class="html-italic">n</span> = 3). Treatments consisted of modified Hoagland’s solution with varying amounts of nitrate and ammonium (mM) and a deionized water treatment (diH<sub>2</sub>O) control. Plots show the mean values with error bars indicating ± standard error of the mean (SEM). Letters represent the result of Tukey’s multiple comparisons test (α = 0.05).</p>
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<p>Root responses to nutrient treatments. (<b>A</b>) Primary root number among treatments (<span class="html-italic">n</span> = 3). (<b>B</b>) Primary root length (cm) among treatments (<span class="html-italic">n</span> = 3). Treatments consisted of modified Hoagland’s solution with varying amounts of nitrate and ammonium (mM) and a deionized water treatment (diH<sub>2</sub>O) control. Plots show the mean values ± SEM. Letters represent the result of Tukey’s multiple comparisons test (α = 0.05).</p>
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<p>Chlorophyll content changes in cladodes in response to nutrient treatments. (<b>A</b>) Chlorophyll a content among treatments (<span class="html-italic">n</span> = 6). (<b>B</b>) Chlorophyll b content among treatments (<span class="html-italic">n</span> = 6). (<b>C</b>) Chlorophyll a + b content among treatments (<span class="html-italic">n</span> = 6). Treatments consisted of modified Hoagland’s solution with varying amounts of nitrate and ammonium (mM) and a deionized water treatment (diH<sub>2</sub>O) control. Plots show the mean values ± SEM. Letters represent the result of Tukey’s multiple comparisons test (α = 0.05).</p>
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<p>Difference between dawn–dusk titratable acidity changes in cladodes in response to nutrient treatments. (<b>A</b>) Titratable acidity to pH = 7.0 (malate equivalents) among treatments (<span class="html-italic">n</span> = 6). (<b>B</b>) Titratable acidity to pH = 7.0 to 8.4 (citrate equivalents) among treatments (<span class="html-italic">n</span> = 6). Treatments consisted of modified Hoagland’s solution with varying amounts of nitrate and ammonium (mM) and a deionized water treatment (diH<sub>2</sub>O) control. Plots show the mean values ± SEM. Letters represent the result of Tukey’s multiple comparisons test (<span class="html-italic">α</span> = 0.05).</p>
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<p>Difference in soluble sugars and starch in cladodes in response to nutrient treatments. (<b>A</b>) Glucose content among treatments (<span class="html-italic">n</span> = 6). (<b>B</b>) Fructose content among treatments (<span class="html-italic">n</span> = 6). (<b>C</b>) Sucrose content among treatments (<span class="html-italic">n</span> = 6). (<b>D</b>) Starch content among treatments (<span class="html-italic">n</span> = 6). Treatments consisted of modified Hoagland’s solution with varying amounts of nitrate and ammonium (mM) and a deionized water treatment (diH<sub>2</sub>O) control. Plots show the mean values ± SEM. Letters represent the result of Tukey’s multiple comparisons test (α = 0.05).</p>
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<p>Difference in nitrate reductase (NR) activity in roots and nitrate, ammonium, and glyoxylic acid content in cladodes in response to nutrient treatments. (<b>A</b>) Root NR activity among treatments (<span class="html-italic">n</span> = 3). (<b>B</b>) Nitrate content among treatments (<span class="html-italic">n</span> = 6). (<b>C</b>) Ammonium content among treatments (<span class="html-italic">n</span> = 6). (<b>D</b>) Glyoxylic acid content among treatments (<span class="html-italic">n</span> = 6). Treatments consisted of modified Hoagland’s solution with varying amounts of nitrate and ammonium (mM) and a deionized water treatment (diH<sub>2</sub>O) control. Plots show the mean values ± SEM. Letters represent the result of Tukey’s multiple comparisons test (α = 0.05).</p>
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<p>Carbon percentage, nitrogen percentage, and carbon/nitrogen ratios in cladodes in response to nutrient treatments. (<b>A</b>) Carbon (%) among treatments (<span class="html-italic">n</span> = 3). (<b>B</b>) Nitrogen (%) among treatments (<span class="html-italic">n</span> = 6). (<b>C</b>) Carbon/nitrogen (C:N) ratios among treatments (<span class="html-italic">n</span> = 6). Treatments consisted of modified Hoagland’s solution with varying amounts of nitrate and ammonium (mM) and a deionized water treatment (diH<sub>2</sub>O) control. Plots show the mean values ± SEM. Letters represent the result of Tukey’s multiple comparisons test (α = 0.05).</p>
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<p>Collective heatmap of CAM-related and N metabolism relative gene expression measured through RT-qPCR analysis among the nitrate and ammonium treatments (mMol). Genes listed: aluminum-activated malate transporter (ALMT_206820), phosphoenolpyruvate carboxylase (PPC_7190), phosphoenolpyruvate carboxykinase (PEPCK_211860), nitrate reductase (NR_52570), nitrite reductase (NiR_241390), glutamate synthase (GOGAT_81140), asparagine synthase (AS_236590), glutamate dehydrogenase (GDH_460, GDH_201910), and glutamine synthetase (GS_30800 and GS_94700). Relative expression of all genes was normalized to the 0 + 0 nitrate and ammonium treatment. The color scale represents actin and ubiquitin normalized log<sub>2</sub> transformed relative counts where blue indicates low expression and red indicates high expression.</p>
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26 pages, 1943 KiB  
Article
Rh(II)/Pd(0) Dual Catalysis: Carbenoid N-H Insertion/Allylation Cascade Reaction to Construct Highly Functionalized and Polysubstituted Pyrrolidines
by Maocheng Tang, Xianyan Jiao, Deping He, Ji-Xing Zhao, Ping Liu and Chun-Tian Li
Molecules 2024, 29(24), 5880; https://doi.org/10.3390/molecules29245880 - 13 Dec 2024
Viewed by 221
Abstract
In the category of drugs approved by the U.S. FDA, pyrrolidine is the most frequently used core of five-membered nonaromatic heterocycles containing nitrogen. Herein, a Rh(II)/Pd(0) dual-catalyzed carbenoid N-H insertion/allylation cascade reaction has been developed. This protocol provide an efficient approach for the [...] Read more.
In the category of drugs approved by the U.S. FDA, pyrrolidine is the most frequently used core of five-membered nonaromatic heterocycles containing nitrogen. Herein, a Rh(II)/Pd(0) dual-catalyzed carbenoid N-H insertion/allylation cascade reaction has been developed. This protocol provide an efficient approach for the construction of diverse highly functionalized and polysubstituted pyrrolidines in high yields (up to 91%) with excellent chemoselectivities and high diastereoselectivities (>20:1) under mild reaction conditions. Full article
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<p>Functionalized compounds with pyrrolidine core structure.</p>
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<p>N-H insertion cascade reactions of metallocarbenes to synthesis of polysubstituted pyrrolidines [<a href="#B29-molecules-29-05880" class="html-bibr">29</a>,<a href="#B31-molecules-29-05880" class="html-bibr">31</a>,<a href="#B32-molecules-29-05880" class="html-bibr">32</a>,<a href="#B33-molecules-29-05880" class="html-bibr">33</a>,<a href="#B35-molecules-29-05880" class="html-bibr">35</a>,<a href="#B36-molecules-29-05880" class="html-bibr">36</a>,<a href="#B39-molecules-29-05880" class="html-bibr">39</a>].</p>
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<p>Plausible mechanism and preferential conformation for transition states.</p>
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<p>Diazo compounds 1, substrate scope. [a] For reaction conditions, see entry 6 of <a href="#molecules-29-05880-t001" class="html-table">Table 1</a>; [b] Isolated yield; [c] Diastereoselectivities were determined by 1H NMR spectroscopy of the crude reaction mixture; N.D. = not detected; d.r. = diastereomeric ratio.</p>
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<p>Application to large-scale synthesis and synthetic transformation.</p>
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<p>Mechanistic control experiments.</p>
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<p>Substrate synthesis method.</p>
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12 pages, 4684 KiB  
Article
Efficient Photocatalytic Removal of Aqueous Ammonia Nitrogen by g-C3N4/CoP Heterojunctions Under Visible Light Illumination
by Dongxu Wang, Wanfeng Mao, Lihong Zhao, Duo Meng, Jiaqi Tang and Tengfei Wu
Nanomaterials 2024, 14(24), 1996; https://doi.org/10.3390/nano14241996 - 13 Dec 2024
Viewed by 381
Abstract
With the development of industry, agriculture, and aquaculture, excessive ammonia nitrogen mainly involving ionic ammonia (NH4+) and molecular ammonia (NH3) has inevitable access to the aquatic environment, posing a severe threat to water safety. Photocatalytic technology shows great [...] Read more.
With the development of industry, agriculture, and aquaculture, excessive ammonia nitrogen mainly involving ionic ammonia (NH4+) and molecular ammonia (NH3) has inevitable access to the aquatic environment, posing a severe threat to water safety. Photocatalytic technology shows great advantages for ammonia nitrogen removal, such as its efficiency, reusability, low cost, and environmental friendliness. In this study, CP (g-C3N4/CoP) composite materials, which exhibited high-efficiency ammonia nitrogen removal, were synthesized through a simple self-assembly method. For the optimal CP-10 (10% CoP) samples, the removal rate of ammonia nitrogen reached up to 94.8% within 80 min under visible light illumination. In addition, the nitrogen selectivity S(N2) is about 60% for all oxidative products. The high performance of the CP-10 photocatalysts can be ascribed to the effective separation and transmission of electron–hole pairs caused by their heterogeneous structure. This research has significance for the application of photocatalysis for the remediation of ammonia nitrogen wastewater. Full article
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<p>XRD patterns of synthesized photocatalysts.</p>
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<p>(<b>a</b>) TEM image; (<b>b</b>–<b>d</b>) HRTEM images of CoP/g-C<sub>3</sub>N<sub>4</sub>.</p>
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<p>(<b>a</b>) Co 2p, (<b>b</b>) P 2p, (<b>c</b>) C 1s, and (<b>d</b>) N 1s XPS spectra of CoP/g-C<sub>3</sub>N<sub>4</sub> photocatalysts.</p>
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<p>(<b>a</b>) UV-vis DRS, (<b>b</b>) band gap energy, (<b>c</b>) photocurrent transient responses, and (<b>d</b>) EIS Nyquist plots.</p>
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<p>(<b>a</b>) Ammonia nitrogen removal rate of prepared photocatalysts and (<b>b</b>) apparent rate constants (k) for ammonia nitrogen removal rate with the prepared photocatalysts.</p>
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<p>The influences of (<b>a</b>) pH value and (<b>b</b>) ionic strength on the removal of ammonia nitrogen.</p>
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<p>(<b>a</b>) Ammonia nitrogen removal under different experimental conditions and (<b>b</b>) percentage of influence of different experimental conditions for ammonia nitrogen removal.</p>
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<p>(<b>a</b>) The removal of ammonia nitrogen over CP-10 photocatalysts in the presence of various scavengers, (<b>b</b>) Mott–Schottky plot of CP-10, (<b>c</b>) schematic band gap structures of prepared photocatalysts, (<b>d</b>) TEMPO-h<sup>+</sup> and (<b>e</b>) DMPO-·OH for S-CN samples, and (<b>f</b>) conversion of inorganic nitrogen in the process of ammonia nitrogen removal.</p>
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<p>Schematic diagram of the possible photocatalytic mechanism of ammonia nitrogen removal.</p>
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11 pages, 4041 KiB  
Article
Enhanced Performance of Ce Doping VW/Ti Catalysts for Synergistic Catalytic Removal of NOx and Chlorobenzene
by Na Zhu, Lingyu Yu, Pengpeng Xu and Yang Deng
Catalysts 2024, 14(12), 919; https://doi.org/10.3390/catal14120919 - 12 Dec 2024
Viewed by 405
Abstract
Nitrogen oxides (NOx) and chlorobenzene (CB) released during waste incineration and iron ore sintering pose significant threats to both the atmosphere and human health, necessitating effective control measures. Vanadium-based catalysts are commonly employed for the simultaneous control of NOx and [...] Read more.
Nitrogen oxides (NOx) and chlorobenzene (CB) released during waste incineration and iron ore sintering pose significant threats to both the atmosphere and human health, necessitating effective control measures. Vanadium-based catalysts are commonly employed for the simultaneous control of NOx and CB; however, their catalytic performance requires further enhancement. In this study, the NH3-SCR activity and CB catalytic oxidation (CBCO) activity were significantly enhanced by doping the V10W/Ti catalyst with Ce. During the multi-pollutant control (MPC) reaction, the optimized 15CeV10W/Ti catalyst demonstrated NOx conversion approaching 100% and N2 selectivity exceeding 95% at temperatures between 210 and 450 °C. Additionally, it achieved CB conversion nearing 100% and CO2 selectivity above 80% at temperatures above 350 °C. These results were markedly superior to those of the conventional commercial 1%V2O5–10%WO3/TiO2 catalyst. Characterization studies indicated that the 15CeV10W/Ti catalyst possessed improved redox performance and more acidic sites. In the MPC reaction, the declined CBCO activity, compared to the CB separate oxidation, can be attributed primarily to the competitive adsorption of NH3 with CB. Conversely, the observed decrease in NOx conversion at lower temperatures was primarily due to the suppression of the oxidation of NO to NO2 by CB. Full article
(This article belongs to the Section Catalytic Materials)
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<p>XRD patterns of 15CeV10W/Ti-X catalysts.</p>
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<p>H<sub>2</sub>-TPR profiles (<b>a</b>) and H<sub>2</sub> consumption (<b>b</b>) of 15CeV10W/Ti-X catalysts.</p>
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<p>XPS spectra of (<b>a</b>) V 2p, (<b>b</b>) O 1s, and (<b>c</b>) Ce 3d for 15CeV10W/Ti-X catalysts.</p>
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<p>NH<sub>3</sub>-TPD profiles of 15CeV10W/Ti-X catalyst.</p>
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<p>NH<sub>3</sub>-SCR activity of 15CeV10W/Ti-X catalysts: (<b>a</b>) NO<span class="html-italic"><sub>x</sub></span> conversion; (<b>b</b>) N<sub>2</sub> selectivity.</p>
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<p>V10W/Ti and 15CeV10W/Ti catalysts: (<b>a</b>) NO<span class="html-italic"><sub>x</sub></span> conversion and (<b>c</b>) N<sub>2</sub> selectivity in the presence/absence of 50 ppm CB, (<b>b</b>) CB conversion, and (<b>d</b>) CO<sub>2</sub> selectivity in the presence/absence of SCR reactants.</p>
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<p>Desorption of (<b>a</b>) NO and (<b>b</b>) NO<sub>2</sub> from NO + O<sub>2</sub>-TPD and NO + O<sub>2</sub> + CB-TPD over V10W/Ti and 15CeV10W/Ti catalysts.</p>
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<p>TPSR curves of (<b>a</b>) V10W/Ti and (<b>b</b>) 15CeV10W/Ti catalysts.</p>
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21 pages, 2925 KiB  
Article
Effects of Different Microplastics on Wheat’s (Triticum aestivum L.) Growth Characteristics and Rhizosphere Soil Environment
by Yan Zhang, Songze Hao, Ping Li, Zhenjie Du, Yuze Zhou, Guohao Wang, Zhijie Liang and Ming Dou
Plants 2024, 13(24), 3483; https://doi.org/10.3390/plants13243483 - 12 Dec 2024
Viewed by 366
Abstract
In order to reveal the effects of microplastics (MPs) on the growth and rhizosphere soil environmental effects of wheat (Triticum aestivum L.), three microplastic types (polypropylene MPs (PP-MPs), high-density polyethylene MPs (HDPE-MPs), and polylactic acid MPs (PLA-MPs)), particle sizes (150, 1000, and [...] Read more.
In order to reveal the effects of microplastics (MPs) on the growth and rhizosphere soil environmental effects of wheat (Triticum aestivum L.), three microplastic types (polypropylene MPs (PP-MPs), high-density polyethylene MPs (HDPE-MPs), and polylactic acid MPs (PLA-MPs)), particle sizes (150, 1000, and 4000 μm), and concentrations (0.1, 0.5, and 1 g·kg−1) were selected for a pot experiment under natural environment conditions. The differences in germination rate (GR), germination inhibition rate (GIR), growth characteristics, physicochemical properties, and enzymatic activities of wheat in rhizosphere soil were analyzed using statistical analysis and variance analysis. The results show that the germination rate of wheat seeds decreased under different MPs, and the HDPE-MPs, medium particle size (1000 μm), and medium concentration (0.5 g·kg−1) had the greatest inhibitory effect on wheat seed germination. The effects of MPs on wheat seed growth characteristics were inconsistent; the germination potential (GP), germination index (GI), and vitality index (VI) showed a significant decreasing trend under the PLA-MPs and medium-concentration (0.5 g·kg−1) treatment, while the mean germination time (MGT) showed a significant increasing trend; the GP and MGT showed a significant decreasing and increasing trend under the high-particle-size (4000 μm) treatment, respectively, while the GI and VI showed a significant decreasing trend under the medium-particle-size (1000 μm) treatment. The growth characteristics of wheat plants showed a significant decreasing trend under different MPs, with the SPAD, nitrogen concentration of the leaves, and plant height decreasing the most under PLA-MP treatment, the SPAD and nitrogen concentration of leaves decreasing the most under low-particle-size (150 μm) and low-concentration (0.1 g·kg−1) treatments, and the decreases in plant height under the high-particle-size (4000 μm) and high-concentration (1 g·kg−1) treatments being the largest. There were significant increasing trends for ammonium nitrogen (NH4+), total phosphorus (TP), soil urease (S-UE), soil acid phosphatase (S-ACP), and soil sucrase (S-SC) under different microplastics, while the PLA-MPs had a significant increasing trend for nitrate nitrogen (NO3) and a significant decreasing trend for pH; there was a significant decreasing trend for total nitrogen (TN) under the HDPE-MPs and PLA-MPs, and for each particle size and concentration, the PLA-MPs and low-concentration (0.1 g·kg−1) treatments showed a significant decreasing trend for soil catalase (S-CAT). The research results could provide certain data and theoretical bases for evaluating the effects of MPs on crop growth and soil ecological environments. Full article
(This article belongs to the Section Plant–Soil Interactions)
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<p><span class="html-italic">GR</span> of wheat seeds under the CK and different microplastic characteristics. (<b>a</b>) Microplastic types. (<b>b</b>) Microplastic particle sizes. (<b>c</b>) Microplastic concentrations. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p><span class="html-italic">GIR</span> of wheat seeds under the CK and different microplastic characteristics. (<b>a</b>) Microplastic types. (<b>b</b>) Microplastic particle sizes. (<b>c</b>) Microplastic concentrations. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Effects on wheat seed growth (<span class="html-italic">GP</span>, <span class="html-italic">GI</span>, <span class="html-italic">VI</span>, and <span class="html-italic">MGT</span>) under the CK and different microplastic characteristics. (<b>a</b>–<b>d</b>) Microplastic types. (<b>e</b>–<b>h</b>) Microplastic particle sizes. (<b>i</b>–<b>l</b>) Microplastic concentrations. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Effects on wheat plant growth (SPAD, nitrogen concentration of the leaves, and plant height) under the CK and different microplastic characteristics. (<b>a</b>–<b>c</b>) Microplastic types. (<b>d</b>–<b>f</b>) Microplastic particle sizes. (<b>g</b>–<b>i</b>) Microplastic concentrations. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Effects on physicochemical properties of wheat rhizosphere soil under the CK and different microplastic types. (<b>a</b>) NH<sub>4</sub><sup>+</sup>, (<b>b</b>) NO<sub>3</sub><sup>−</sup>, (<b>c</b>) TN, (<b>d</b>) TP, (<b>e</b>) pH, (<b>f</b>) EC, and (<b>g</b>) OM. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Effects on physicochemical properties of wheat rhizosphere soil under the CK and different microplastic particle sizes. (<b>a</b>) NH<sub>4</sub><sup>+</sup>, (<b>b</b>) NO<sub>3</sub><sup>−</sup>, (<b>c</b>) TN, (<b>d</b>) TP, (<b>e</b>) pH, (<b>f</b>) EC, and (<b>g</b>) OM. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Effects on physicochemical properties of wheat rhizosphere soil under the CK and different microplastic concentrations. (<b>a</b>) NH<sub>4</sub><sup>+</sup>, (<b>b</b>) NO<sub>3</sub><sup>−</sup>, (<b>c</b>) TN, (<b>d</b>) TP, (<b>e</b>) pH, (<b>f</b>) EC, and (<b>g</b>) OM. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Effects on enzymatic activities of wheat rhizosphere soil under the CK and different microplastic types. (<b>a</b>) S-UE, (<b>b</b>) S-ACP, (<b>c</b>) S-SC, (<b>d</b>) S-CAT, and (<b>e</b>) S-DHA. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Effects on enzymatic activities of wheat rhizosphere soil under the CK and different microplastic particle sizes. (<b>a</b>) S-UE, (<b>b</b>) S-ACP, (<b>c</b>) S-SC, (<b>d</b>) S-CAT, and (<b>e</b>) S-DHA. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Effects on enzymatic activities of wheat rhizosphere soil under the CK and different microplastic concentrations. (<b>a</b>) S-UE, (<b>b</b>) S-ACP, (<b>c</b>) S-SC, (<b>d</b>) S-CAT, and (<b>e</b>) S-DHA. All data are presented as the mean ± SD (n ≥ 3 biological replicates). Lowercase letters above bars indicate significant differences according to the post hoc Fisher LSD test (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Concept and actual image of pot experiment design.</p>
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