Screening of multiclass pesticide residues in maca and Moringa oleifera by a modified QuEChERS sample preparation procedure and UPLC-ESI-MS/MS analysis

In the present study, a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was proposed for the simultaneous analysis of 75 pesticides in maca and Moringa oleifera with ultra-performance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-ESI-MS/MS). The developed method was validated in accordance with linearity, linear range, limit of detection, limit of quantification, accuracy, precision, and matrix effect. Each analyte had good linearity (R² > 0.99) in the corresponding concentration range. The method LOD and LOQ values of all the analytes ranged from 0.01 μg kg⁻¹ to 303.35 μg kg⁻¹ and 0.03 μg kg⁻¹ to 1011.15 μg kg⁻¹, respectively. The recoveries (n = 6) of the analyzed pesticides were in the range of 75.92–113.43%. The RSDs of precision were between 0.60% and 7.36%. All matrix effect values ranged from 81.79% to 118.71% and 80.36% to 119.64% in maca and Moringa oleifera, respectively. The analysis of 103 samples showed the presence of isofenphos-methyl in some of them. The method had a good application prospect and could be used as a general approach for the quantitative determination of pesticide residues in food.

In the present study, a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was proposed for the simultaneous analysis of 75 pesticides in maca and Moringa oleifera with UPLC-ESI-MS/MS.     

Total and bioaccessible heavy metals in cabbage from major producing cities in Southwest China: health risk assessment and cytotoxicity

Green leafy vegetables are economical and nutritious, but they may be contaminated with heavy metals. In this study, we assessed the total and bioaccessible concentrations of As, Cd, Pb and Cr in a popular vegetable cabbage (Brassica oleracea) from four major producing cities in Yunnan, Southwest China. With the mean concentrations of As, Cd, Pb and Cr being 0.24, 0.20, 0.32 and 1.28 mg kg⁻¹, the As, Cd and Pb concentrations were within the limits of 0.2–0.5 mg kg⁻¹ based on Chinese National Standards and the WHO/FAO, but Cr concentration was 2.6-times greater than the limit of 0.5 mg kg⁻¹. Based on an in vitro bioaccessibility assay of the Solubility Bioaccessibility Research Consortium (SBRC), As bioaccessibility was the lowest at 11% while those of Cd, Pb and Cr were much greater at 68–87%. The estimated daily intake (EDI) of metals through cabbage ingestion was similar for children and adults. Among the four metals, only Cr''s EDI at 2.29–1.87 exceeded 1 based on total and bioaccessible concentrations. The high Cr concentration at 1.28 mg kg⁻¹ coupled with its high bioaccessibility at 67.5% makes Cr of concern in cabbage. However, human gastrointestinal cells exposed to the gastric digesta with high bioaccessible heavy metals and risky EDI, showed no obvious cytotoxicity, indicating that existing models based on total or bioaccessible heavy metals may overestimate their human health risk. Taken together, to accurately assess the human health risk of heavy metals in cabbage, both total/bioaccessible concentrations and the gastrointestinal cell responses should be considered.

We analyzed the total and bioaccessible concentrations of heavy metals in a popular vegetable cabbage (Brassica oleracea) from producing cities in Yunnan, Southwest China and assessed their health risk based on both bioaccessibility and cytotoxicity.     

Simultaneous determination of 114 pesticides in complex Chinese herbal medicine Fritillaria using ordered mesoporous carbon CMK-3 as a reversed-dispersive solid phase extraction sorbent

Fritillaria, a traditional Chinese herbal medicine, is classified into many medicinal species and contains numerous complex components. It is thus difficult to simultaneously detect multiple pesticide residues in different Fritillaria species. An easy, reliable, and widely applicable analytical method based on a modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method coupled with LC-MS/MS was developed to solve these problems encountered during pesticide residue analysis in complex Fritillaria matrices. Ordered mesoporous carbon CMK-3 and a primary secondary amine (PSA) were used as efficient purification sorbents by optimization of the QuEChERS process. Systematic method validation was performed for four species of Fritillaria. The matrix effect of pesticides varied among different Fritillaria species, and matrix-matched standard solutions were thus employed for quantitative analysis. The mean recoveries of all pesticides ranged from 88.6% to 95.5%, with mean relative standard deviations (RSD) lower than 6% at spiked concentrations of 30, 120, and 240 μg kg⁻¹. The limits of quantification (LOQ) for the developed method were in the range of 30–120 μg kg⁻¹. This method was further used to analyze 47 Fritillaria samples from Zhejiang province, China, and seven pesticides were detected in 22 Fritillaria samples. These results demonstrate that the developed method is suitable for an accurate analysis of multiple pesticide residues in various Fritillaria.

Fritillaria, a traditional Chinese herbal medicine, is classified into many medicinal species and contains numerous complex components.     

Hierarchical Ni–Co–Mn hydroxide hollow architectures as high-performance electrodes for electrochemical energy storage

In this study, hierarchical Ni–Co–Mn hydroxide hollow architectures were successfully achieved via an etching process. We first performed the synthesis of NiCoMn-glycerate solid spheres via a solvothermal route, and then NiCoMn-glycerate as the template was etched to convert into hierarchical Ni–Co–Mn hydroxide hollow architectures in the mixed solvents of water and 1-methyl-2-pyrrolidone. Hollow architectures and high surface area enabled Ni–Co–Mn hydroxide to manifest a specific capacitance of 1626 F g⁻¹ at 3.0 A g⁻¹, and it remained as large as 1380 F g⁻¹ even at 3.0 A g⁻¹. The Ni–Co–Mn hydroxide electrodes also displayed notable cycle performance with a decline of 1.6% over 5000 cycles at 12 A g⁻¹. Moreover, an asymmetric supercapacitor assembled with this electrode exhibited an energy density of 44.4 W h kg⁻¹ at 1650 W kg⁻¹ and 28.5 W h kg⁻¹ at 12 374 W kg⁻¹. These attractive results demonstrate that hierarchical Ni–Co–Mn hydroxide hollow architectures have broad application prospects in supercapacitors.

An effective etching method is developed for the synthesis of hierarchical Ni–Co–Mn hydroxide hollow architectures, which exhibit high performance in electrochemical energy storage.     

Flowery nickel–cobalt hydroxide via a solid–liquid sulphur ion grafting route and its application in hybrid supercapacitive storage

In our research, a two-step solid–liquid route was employed to fabricate flowery nickel–cobalt hydroxide with sulphur ion grafting (Ni1Co2–S). The utilization of NaOH/agar and Na₂S/agar could efficiently retard the release rates of OH⁻ or S²⁻ ions at the solid–liquid interface due to strong bonding between agar hydrogel and these anions. Ni1Co2–S generally displays ultrathin flowery micro-frame, ultrathin internal nanosheets and expanded pore size. Besides, the introduction of suitable sulphide species into nickel–cobalt hydroxide could improve its conductivity due to the lower band gap of Ni–Co sulphide. The supercapacitive electrode Ni1Co2–S presented capacitance of 1317.8 F g⁻¹ (at 1 A g⁻¹) and suitable rate performance (77.9% at 10 A g⁻¹ and 59.3% at 20 A g⁻¹). Furthermore, a hybrid supercapacitor (HSC) was developed utilizing positive Ni1Co2–S and negative activated carbon electrodes. As expected, the HSC device exhibited excellent specific capacitance (117.1 F g⁻¹ at 1 A g⁻¹), considerable energy densities (46.7 W h kg⁻¹ at 0.845 kW kg⁻¹ and 27.5 W h kg⁻¹ even at 9 kW kg⁻¹) and suitable cycling performance, which further illuminated the high energy storage capacity of Ni1Co2–S.

The Ni1Co2–S material fabricated via a solid–liquid route achieves high-performance supercapacitive storage.     

Heavy metal pollution and human health risk assessment at mercury smelting sites in Wanshan district of Guizhou Province,China

The Wanshan district of Guizhou Province has a long history of mercury mining and smelting. Previous studies have been carried out on heavy metal (HM) pollution in the soil around Wanshan (such as in urban and farmland areas), but these studies have not been conducted at mercury smelting sites. In this study, the distribution characteristics of As, Be, Cd, Cr, Cu, Hg, Ni, Sb, Pb and Zn and their sources in the shallow stratum (<10 m) of the mercury smelting site in the Wanshan district were analyzed. Human health risks were evaluated using deterministic risk assessment (DRA) and probabilistic risk assessment (PRA) models. The contribution rates of different HM sources to human health risks were also calculated. The maximum HM concentration in mercury smelting site soil occured in the shallow soil (0–1 m), and the concentration sequences were as follows: 358.51 mg kg⁻¹ (Hg) > 248.6 mg kg⁻¹ (Zn) > 67.42 mg kg⁻¹ (As) > 59.04 mg kg⁻¹ (Ni) > 57.56 mg kg⁻¹ (Pb) > 49.59 mg kg⁻¹ (Cr) > 46.65 mg kg⁻¹ (Sb) > 15.65 mg kg⁻¹ (Cu) > 2.02 mg kg⁻¹ (Be) > 0.78 mg kg⁻¹ (Cd). The variable coefficients (CVs) were 1.64 (As), 0.67 (Be), 3.15 (Cd), 1.89 (Cr), 0.95 (Cu), 3.08 (Hg), 0.79 (Ni), 1.41 (Sb), 0.68 (Pb) and 1.13 (Zn), respectively. The HM concentrations in deep soils (9 m) still exceed the local background values, suggesting that heavy metals in shallow soil have migrated downward in the site. Three pollution sources identified with the shallow soil (0–1 m) HMs using the positive matrix factorization (PMF) model, were mercury smelting and coal combustion mixed sources (As, Hg and Zn), parent material sources (Ni, Cu, Cr, Cd and Sb) and wastewater discharge sources (Cu and Pb), respectively. DRA indicated that oral ingestion was the main pathway affecting the carcinogenic risk (CR) and hazard quotient (HQ) of heavy metals. The total-CR of twenty-five sampling points is between 1.219 × 10⁻⁶ and 3.446 × 10⁻⁴, and the total-HQ is between 0.37 and 43.56. PRA results indicated that DRA will underestimate the health risk of all populations in Guizhou Province, especially female, and BW_a is the most influential variable for the PRA results. Smelting and coal combustion mixed sources contributed the most CR (99.29%) and with an HQ of 89.38% were the major sources of pollution affecting human health.

The DRA model was used to analyze the human health risk contribute of different HMs sources in the mercury smelting site, and the PRA model was used to verify.     

Biosorption and bioaccumulation characteristics of cadmium by plant growth-promoting rhizobacteria

Plant growth-promoting rhizobacteria (PGPR) not only promote growth and heavy metal uptake by plants but are promising biosorbents for heavy metals remediation. However, there exist arguments over whether extracellular adsorption (biosorption) or intracellular accumulation (bioaccumulation) play dominant roles in Cd(ii) adsorption. Therefore, three cadmium-resistant PGPR, Cupriavidus necator GX_5, Sphingomonas sp. GX_15, and Curtobacterium sp. GX_31 were used to study bioaccumulation and biosorption mechanisms under different initial Cd(ii) concentrations, using batch adsorption experiments, desorption experiments, scanning electron microscopy coupled with energy dispersive X-ray (SEM-EDX) spectroscopy, transmission electron microscopy (TEM), and Fourier-transform infrared (FTIR) spectroscopy. In this study, with the increase of the initial Cd(ii) concentrations, the removal efficiency of strains decreased and the adsorption capacity improved. The highest Cd(ii) removal efficiency values were 25.05%, 53.88%, and 86.06% for GX_5, GX_15, and GX_31 with 20 mg l⁻¹ of Cd(ii), while the maximum adsorption capacity values were 7.97, 17.13, and 26.43 mg g⁻¹ of GX_5, GX_15, and GX_31 with 100 mg l⁻¹ of Cd(ii). Meanwhile, the removal efficiency and adsorption capacity could be ordered as GX_31 > GX_15 > GX_5. The dominant adsorption mechanism for GX_5 was bioaccumulation (50.66–60.38%), while the dominant mechanisms for GX_15 and GX_31 were biosorptions (60.29–64.89% and 75.93–79.45%, respectively). The bioaccumulation and biosorption mechanisms were verified by SEM-EDX, TEM and FTIR spectroscopy. These investigations could provide a more comprehensive understanding of metal-bacteria sorption reactions as well as practical application in remediation of heavy metals.

Plant growth-promoting rhizobacteria (PGPR) not only promote growth and heavy metal uptake by plants but are promising biosorbents for heavy metals remediation.     

In situ hydrothermal synthesis of nickel cobalt sulfide nanoparticles embedded on nitrogen and sulfur dual doped graphene for a high performance supercapacitor electrode

Nickel cobalt sulfide nanoparticles (NCS) embedded onto a nitrogen and sulfur dual doped graphene (NS-G) surface are successfully synthesized via a two-step facile hydrothermal process. The electrical double-layer capacitor of NS-G acts as a supporting host for the growth of pseudocapacitance NCS nanoparticles, thus enhancing the synergistic electrochemical performance. The specific capacitance values of 1420.2 F g⁻¹ at 10 mV s⁻¹ and 630.6 F g⁻¹ at 1 A g⁻¹ are achieved with an impressive capability rate of 76.6% preservation at 10 A g⁻¹. Furthermore, the integrating NiCo₂S₄ nanoparticles embedding onto the NS-G surface also present a surprising improvement in the cycle performance, maintaining 110% retention after 10 000 cycles. Owing to the unique morphology an impressive energy density of 19.35 W h kg⁻¹ at a power density of 235.0 W kg⁻¹ suggests its potential application in high-performance supercapacitors.

Newly developed in situ hydrothermal synthesis governs morphology of Ni–Co–S embedded on N–S doped graphene thus providing exceptional capacitive behavior.     

One-step production of N–O–P–S co-doped porous carbon from bean worms for supercapacitors with high performance

In recent years, multi-heteroatom-doped hierarchical porous carbons (HPCs) derived from natural potential precursors and synthesized in a simple, efficient and environmentally friendly manner have received extensive attention in many critical technology applications. Herein, bean worms (BWs), a pest in bean fields, were innovatively employed as a precursor via a one-step method to prepare N–O–P–S co-doped porous carbon materials. The pore structure and surface elemental composition of carbon can be modified by adjusting KOH dosage, exhibiting a high surface area (S_BET) of 1967.1 m² g⁻¹ together with many surface functional groups. The BW-based electrodes for supercapacitors were shown to have a good capacitance of up to 371.8 F g⁻¹ in 6 M KOH electrolyte at 0.1 A g⁻¹, and good rate properties with 190 F g⁻¹ at a high current density of 10 A g⁻¹. Furthermore, a symmetric supercapacitor based on the optimal carbon material (BWPC_1/3) was also assembled with a wide voltage window of 2.0 V, demonstrating satisfactory energy density (27.5 W h kg⁻¹ at 200 W kg⁻¹) and electrochemical cycling stability (97.1% retention at 10 A g⁻¹ over 10 000 charge/discharge cycles). The facile strategy proposed in this work provides an attractive way to achieve high-efficiency and scalable production of biomass-derived HPCs for energy storage.

Bean worms, a pest in bean fields, were innovatively employed as a precursor via a one-step method to prepare N–O–P–S co-doped porous carbon materials.     

A novel resource utilization method using wet magnesia flue gas desulfurization residue for simultaneous removal of ammonium nitrogen and heavy metal pollutants from vanadium containing industrial wastewater

In the present study, a novel resource utilization method using wet magnesia flue gas desulfurization (FGD) residue for the simultaneous removal of ammonium nitrogen (NH₄–N) and heavy metal pollutants from vanadium (V) industrial wastewater was proven to be viable and effective. In this process, the wet magnesia FGD residue could not only act as a reductant of hexavalent chromium [Cr(vi)] and pentavalent vanadium [V(v)], but also offered plenty of low cost magnesium ions to remove NH₄–N using struvite crystallization. The optimum experimental conditions for Cr(vi) and V(v) reduction are as follows: the reduction pH = 2.5, the wet magnesia FGD residue dose is 42.5 g L⁻¹, t = 15.0 min. The optimum experimental conditions for NH₄–N and heavy metal pollutants removal are as follows: the precipitate pH = 9.5, the n(Mg²⁺) : n(NH₄⁺) : n(PO₄³⁻) = 0.3 : 1.0 : 1.0, t = 20.0 min. Finally the NH₄–N, V and Cr were separated from the vanadium containing industrial wastewater by forming the difficult to obtain, soluble coprecipitate containing struvite and heavy metal hydroxides. The residual pollutant concentrations in the wastewater were as follows: Cr(vi) was 0.047 mg L⁻¹, total Cr was 0.1 mg L⁻¹, V was 0.14 mg L⁻¹, NH₄–N was 176.2 mg L⁻¹ (removal efficiency was about 94.5%) and phosphorus was 14.7 mg L⁻¹.

A novel resource utilization method using wet magnesia flue gas desulfurization residue for the simultaneous removal of ammonium nitrogen and heavy metal pollutants from vanadium industrial wastewater was proven to be viable and effective.     

Micranthanosides I and II,two novel 1,10-secograyanane diterpenoids and their antinociceptive analogues from the leaves and twigs of Rhododendron micranthum

Micranthanosides I and II (1–2), two diterpenoid glucosides featuring a new 1,10-secograyanane skeleton, thirteen new diterpenoid glycosides (3–15), and 21 known analogues were obtained from the ethanol extract of the leaves and twigs of Rhododendron micranthum. Micranthanoside XII (12) represent the first example of 3,5-epoxy-4,5-seco-ent-kaurane diterpenoid. The structures of these compounds were determined by spectroscopic data analysis and quantum chemical calculations. To clarify the chemical basis and provide reference for rational use of this medicinal plant, the antinociceptive and the anti-inflammatory activities of the compounds were tested. In the acetic acid-induced writhing test, compounds 17 and 19 showed significant antinociceptive activity at a dose of 3 mg kg⁻¹ and compounds 2, 6 and 32 showed significant antinociceptive activity at a dose of 10 mg kg⁻¹. Toxic reactions such as nausea and convulsion were observed when 17, 19, 29, and 31 at a dose of 10 mg kg⁻¹ or 30 and 33 at a dose of 1 mg kg⁻¹ were administered. The anti-inflammatory activities of the isolated compounds were evaluated by measuring the inhibitory effects of LPS-induced NO production in BV2 cells. At 10 μM, micranthanoside IX (9) and rhodomicranoside F (26) showed moderate anti-inflammatory activities with inhibition rates of 56.31% and 72.43%, respectively.

Two unusual diterpenoids with a new 1,10-secograyanane skeleton and thirteen new analogues from the leaves and twigs of Rhododendron micranthum were obtained.     

Unraveling the potential of pesticide-tolerant Pseudomonas sp. augmenting biological and physiological attributes of Vigna radiata (L.) under pesticide stress

In the agricultural domain, chemical pesticides are repetitively and harshly used to kill harmful pests, but they often pose a serious threat to microbial diversity, soil fertility and agricultural output. To deal with these problems, pesticide-tolerant plant growth promoting (PGP) rhizobacterial strains are often used to combat pesticidal toxicity. Here, Pseudomonas sp. PGR-11 (accession no. {"type":"entrez-nucleotide","attrs":{"text":"OM348534","term_id":"2182243475","term_text":"OM348534"}}OM348534), recovered from a Vigna radiata (L.) rhizosphere, produced various growth regulating (GR) substances, including indole-3-acetic acid (IAA; 82.5 ± 9.2 μg mL⁻¹), enzyme 1-aminocyclopropane 1-carboxylate (ACC) deaminase (μM α-ketobutyrate mg⁻¹ protein h⁻¹), siderophores and ammonia. Strain PGR-11 grew well when cultured in growth medium with added metalaxyl (MTXL; 1200 μg mL⁻¹), carbendazim (CBZM; 800 μg mL⁻¹) and tebuconazole (TBZL; 1600 μg mL⁻¹). Pseudomonas sp. synthesized PGP substances even in the presence of increasing doses of pesticides. The phytotoxicity of the tested pesticides was assessed both in vitro and under pot-house conditions using a Vigna radiata (L.) crop. Increasing concentrations of chemical pesticides negatively impacted the growth, physiological and biochemical features. However, pesticide-tolerant Pseudomonas sp. relieved the toxicity and improved the biological attributes of the plant. Bio-inoculated plants showed significant enhancement in germination attributes, dry biomass, symbiotic features and yield features when compared to un-inoculated ones. Furthermore, with 100 μg metalaxyl kg⁻¹ soil, strain PGR-11 increased the chl-a, chl-b, total chlorophyll, carotenoids, SPAD index, photosystem efficiency (Fv/Fm), PSII quantum yield (FPSII), photochemical quenching (qP) and non-photochemical quenching (NpQ) content by 12, 19, 16, 27, 34, 41, 26, 29 and 33%, respectively, over un-inoculated but pesticide-treated plants. Additionally, inoculation of Pseudomonas sp. with 100 μg tebuconazole kg⁻¹ soil caused a significant (p ≤ 0.05) enhancement in transpiration rate (E), stomatal conductance (g_s), photosynthetic rate (P_N), vapor pressure deficit (kPa) and internal CO₂ concentration (C_i) of 19, 26, 23, 28 and 34%, respectively. Conclusively, the power to tolerate abnormally high pesticide concentration, the capacity to produce/secrete PGP substances even in a pesticide-stressed medium and the potential for improving/increasing the growth and physiology of plants by pesticide detoxification makes Pseudomonas sp. PGR-11 a fascinating choice for augmenting the productivity of V. radiata (L.) even in pesticide-stressed soils. The current findings will be helpful for exploring pesticide-tolerant ACC-deaminase-positive microbial strains as gifted entities for the environmental bioremediation of pesticides.

In the agricultural domain, chemical pesticides are repetitively and harshly used to kill harmful pests, but they often pose a serious threat to microbial diversity, soil fertility and agricultural output.     

An ultrasound-assisted approach to bio-derived nanoporous carbons: disclosing a linear relationship between effective micropores and capacitance

Ultrasound irradiation is a technique that can induce acoustic cavitation in liquids, leading to a highly interactive mixture of reactants. In pursuit of high-performance and cost-effective supercapacitor electrodes, pore size distributions of carbonaceous materials should be carefully designed. Herein, fruit skins (mango, pitaya and watermelon) are employed as carbon precursors to prepare nanoporous carbons by the ultrasound-assisted method. Large BET specific surface areas of the as-prepared carbons (2700–3000 m² g⁻¹) are reproducible with pore diameters being concentrated at about 0.8 nm. Among a suite of the bio-derived nanoporous carbons, one reaches a maximum specific capacitance of up to 493 F g⁻¹ (at 0.5 A g⁻¹ in 6 M KOH) in the three-electrode system and achieves high energy densities of 27.5 W h kg⁻¹ (at 180 W kg⁻¹ in 1 M Na₂SO₄) and 10.9 W h kg⁻¹ (at 100 W kg⁻¹ in 6 M KOH) in the two-electrode system. After 5000 continuous charge/discharge cycles, the capacitances maintain 108% in 1 M Na₂SO₄ and 98% in 6 M KOH, exhibiting long working stability. Moreover, such high capacitive performance can be attributed to the optimization of surface areas and pore volumes of the effective micropores (referred to as 0.7–2 nm sized pores). Notably, specific capacitances have been found linearly correlated with surface areas and pore volumes of the effective micropores rather than those of any other sized pore (i.e., <0.7, 2–50 and 0.5–50 nm). Consequently, the fit of electrolyte ions into micropore frameworks should be an important consideration for the rational design of nanopore structures in terms of supercapacitor electrodes.

There is a linear relationship between the effective micropore volume (surface area) and the specific capacitance of bio-derived nanoporous carbons, regardless of biomass type and activation temperature employed.     

Inhibition effect of ZrF4 on UO2 precipitation in the LiF–BeF2 molten salt

The dissolution–precipitation behavior of zirconium dioxide (ZrO₂) in molten lithium fluoride–beryllium fluoride (LiF–BeF₂, (2 : 1 mol, FLiBe)) eutectic salt at 873 K was studied. The results of the dissolution experiment showed that the saturated solubility of ZrO₂ in the FLiBe melt was 3.84 × 10⁻³ mol kg⁻¹ with equilibrium time of 6 h, and its corresponding apparent solubility product (K′_sp) was 3.40 × 10⁻⁵ mol³ kg⁻³. The interaction between Zr(iv) and O²⁻ was studied by titrating lithium oxide (Li₂O) into the FLiBe melt containing zirconium tetrafluoride (ZrF₄), and the concentration of residual Zr(iv) in the melt gradually decreased due to precipitate formation. The precipitate corresponded to ZrO₂, as confirmed by the stoichiometric ratio and X-ray diffraction analysis. The K′_sp was 3.54 × 10⁻⁵ mol³ kg⁻³, which was highly consistent with that from the dissolution experiment. The obtained K′_sp of ZrO₂ was in the same order of magnitude as that of uranium dioxide (UO₂), indicating that a considerable amount of ZrF₄ could inhibit the UO₂ formation when oxide contamination occurred in the melt containing ZrF₄ and uranium tetrafluoride (UF₄). Further oxide titration in the LiF–BeF₂–ZrF₄ (5 mol%)–UF₄ (1.2 mol%) system showed that ZrO₂ was formed first with O²⁻ addition less than 1 mol kg⁻¹, and the precipitation of UO₂ began only after the O²⁻ addition reached 1 mol kg⁻¹ and the precipitation of ZrO₂ decreased the ZrF₄ concentration to 0.72 mol kg⁻¹ (3 mol%). Lastly, UO₂ and ZrO₂ coprecipitated with further O²⁻ addition of more than 1 mol kg⁻¹. The preferential formation of ZrO₂ effectively avoided the combination of UF₄ and O²⁻. This study provides a solution for the control of UO₂ precipitation in molten salt reactors.

This study provides an effective solution for controlling and monitoring the nuclear fuel precipitation (UO₂) in molten fluorides, which is of great importance for the safe operation and fuel salt design of molten salt reactor (MSR).     

Determination and distribution of pesticides and antibiotics in agricultural soils from northern China

Different types of soil samples from a typical farmland in northern China were collected and evaluated for the presence of the pesticides and antibiotics. 47 pesticides were extracted with a quick, easy, cheap, effective, rugged, and safe (QuEChERS) preparation method and cleanup with 50 mg C₁₈, while 10 antibiotics were extracted with methanol/EDTA–McIlvaine buffer solution (v/v = 1/1), then both of them were analyzed with high performance liquid chromatography-tandem mass spectrometer (HPLC-MS/MS). Total concentrations of the 47 pesticides in the soil samples ranged from not detectable (ND) to 3.8 mg kg⁻¹. The soil exhibited relatively high ecological risk for atrazine, chlorpyrifos, tebuconazole, difenoconazole, pymetrozine, and thiamethoxam, as over 1.0% of the sample concentrations exceeded 0.1 mg kg⁻¹. The residual levels of the 10 antibiotics were relatively low (ND-951.0 μg kg⁻¹). Tetracyclines exhibited a high detection rate (20.9%), with 2.8% of the soil samples exhibiting tetracyclines concentrations exceeding 100 μg kg⁻¹, implying high ecological risk. The 4 sulfonamides and 2 macrolides analyzed showed detection rates below 0.8%. Spatial changes in the distribution of pesticides and antibiotics appear to be related to land use patterns, particularly orchards and vegetable plots. The over-standard rate of pesticides and antibiotics in orchards was greater than that of vegetable plots, and grain fields had the lowest over-standard rate. These data were helpful to figure out the pollution of these pesticides and antibiotics, and provided valuable information for soil quality assessment and risk assessment.

Different types of soil samples from a typical farmland in northern China were collected and evaluated for the presence of the pesticides and antibiotics.     

Pseudocapacitance electrode and asymmetric supercapacitor based on biomass juglone/activated carbon composites

A novel electrode material incorporating renewable biomass-derived juglone biomolecules with commercial activated carbon (AC) granules has been through simple ultrasonic dispersion and dissolution–recrystallization and was found to exhibit good electrochemical performance. The juglone biomolecules are prepared by an ultrasound-assisted extraction method from abandoned walnut peel, which decreases pollution and increases economic efficiency. Through the dissolution–recrystallization process with AC, a hierarchical structure with nanosized juglone particles was obtained, and the AC particles worked as scaffolding to strengthen the slight biomolecules, thus expanding the active sites and effectively reducing the dissolution of the active materials. The pseudocapacitance fading mechanism was investigated by ex situ FTIR measurement and the porous structure ensures that the composite electrode has an enhanced specific capacitance of 248 F g⁻¹ compared to 172.8 and 62.5 F g⁻¹ for the respective AC and juglone samples. Besides, the excellent cyclic stability (retained 75% after 3000 charge–discharge cycles) was demonstrated. The highest area-specific capacitance of the composites was 1300 mF cm⁻². An asymmetric supercapacitor based on this composite electrode was assembled with an AC electrode as the counter electrode and exhibited good cyclic performance at a voltage of 1.2 V (retained 77% after 3000 charge–discharge cycles), which provides a high energy density of 12 W h kg⁻¹ at a power density of 0.18 kW kg⁻¹ and a high power density of 2 kW kg⁻¹ at an energy density of 9 W h kg⁻¹. This work explores the application of biomolecule-based composites in energy storage devices and provides a potential strategy for constructing environmentally friendly electrodes.

A strategy for transforming abandoned walnut peel to excellent pseudocapacitance material. The activated carbon reshapes and anchors the juglone, which combined the EDLC and pseudocapacitance to achieve high electrochemical performance.     

Free-standing graphene/bismuth vanadate monolith composite as a binder-free electrode for symmetrical supercapacitors

Preparation of new types of electrode material is of great importance to supercapacitors. Herein, a graphene/bismuth vanadate (GR/BiVO₄) free-standing monolith composite has been prepared via a hydrothermal process. Flexible GR sheets act as a skeleton in the GR/BiVO₄ monolith composites. When used as a binder-free electrode in a three-electrode system, the GR/BiVO₄ composite electrode can provide an impressive specific capacitance of 479 F g⁻¹ in a potential window of −1.1 to 0.7 V vs. SCE at a current density of 5 A g⁻¹. A symmetrical supercapacitor cell which can be reversibly charged–discharged at a cell voltage of 1.6 V has been assembled based on this GR/BiVO₄ monolith composite. The symmetrical capacitor can deliver an energy density of 45.69 W h kg⁻¹ at a power density of 800 W kg⁻¹. Moreover, it ensures rapid energy delivery of 10.75 W h kg⁻¹ with a power density of 40 kW kg⁻¹.

A symmetrical supercapacitor with a high energy density has been assembled based on a free-standing GR/BiVO₄ monolith composite.     

MoS42− intercalated NiFeTi LDH as an efficient and selective adsorbent for elimination of heavy metals

The enormous increase of heavy metal pollution has led to a rise in demand for synthesizing efficient and stable adsorbents for its treatment. Therefore, we have designed a novel adsorbent by introducing (MoS₄)²⁻ moieties within the layers of NiFeTi LDH-NO₃, via an ion exchange mechanism, as a stable and efficient adsorbent to deal with the increasing water pollution due to heavy metals. Characterization techniques such as XRD, FTIR, TGA, SEM, TEM, and Raman spectroscopy were used to confirm the formation of (MoS₄)²⁻ intercalated NiFeTi LDH and structural changes after the adsorption process. The efficiency of the material was tested with six heavy metal ions, among which it was found to be effective for toxic Pb²⁺ and Ag⁺ ions. When selectivity was studied with all six of the metal ions copresent in one solution, the material showed greater selectivity for Pb²⁺ and Ag⁺ ions with the selectivity order of Ni²⁺ < Cu²⁺ < Zn²⁺ < Fe³⁺ < Pb²⁺ < Ag⁺, with great adsorption capacities of 653 mg g⁻¹ for Pb²⁺ and 856 mg g⁻¹ for Ag⁺ metal ions. Further, the kinetics adsorption study for both the metal ions had a great correlation with the pseudo-second-order model and supported the chemisorption process via the formation of M–S bonding. The adsorption process obeyed the Langmuir model. Therefore, the MoS₄-LDH material could be a promising adsorbent for the removal of heavy metals.

Elimination of the heavy metals by using the MoS₄-LDH adsorbent.     

A simple strategy to prepare a layer-by-layer assembled composite of Ni–Co LDHs on polypyrrole/rGO for a high specific capacitance supercapacitor

A facile and novel electrode material of nickel–cobalt layered double hydroxides (Ni–Co LDHs) layered on polypyrrole/reduced graphene oxide (PPy/rGO) is fabricated for a symmetrical supercapacitor via chemical polymerization, hydrothermal and vacuum filtration. This conscientiously layered composition is free from any binder or surfactants which is highly favorable for supercapacitors. The PPy/rGO serves as an ideal backbone for Ni–Co LDHs to form a free-standing electrode for a high-performance supercapacitor and enhanced the overall structural stability of the film. The well-designed layered nanostructures and high electrochemical activity from the hexagonal-flakes like Ni–Co LDHs provide large electroactive sites for the charge storage process. The specific capacitance (1018 F g⁻¹ at 10 mV s⁻¹) and specific energy (46.5 W h kg⁻¹ at 464.9 W kg⁻¹) obtained for the PPy/rGO|Ni–Co LDHs symmetrical electrode in the current study are the best reported for the two-electrode system for PPy- and LDHs-based composites. The outstanding performance in the prepared LBL film is a result of the LBL architecture of the film and the combined effect of redox reaction and electrical double layer capacitance.

A facile and novel electrode material of nickel–cobalt layered double hydroxides (Ni–Co LDHs) layered on polypyrrole/reduced graphene oxide (PPy/rGO) is fabricated for a symmetrical supercapacitor via chemical polymerization, hydrothermal and vacuum filtration.     

Influence of Ni content on structural,magnetocaloric and electrical properties in manganite La0.6Ba0.2Sr0.2Mn1−xNixO3 (0 ≤ x ≤ 0.1) type perovskites

We present a detailed study on the physical properties of La_0.6Ba_0.2Sr_0.2Mn_1−xNi_xO₃ samples (x = 0.00, 0.05 and 0.1). The ceramics were fabricated using the sol–gel route. Structural refinement, employing the Rietveld method, disclosed a rhombohedral R$\bar{3}$c phase. The magnetization vs. temperature plots show a paramagnetic–ferromagnetic (PM–FM) transition phase at the T_C (Curie temperature), which decreases from 354 K to 301 K. From the Arrott diagrams M²vs. μ₀H/M, we can conclude the phase transition is of the second order. Based on measurements of the isothermal magnetization around T_C, the magnetocaloric effects (MCEs) have been calculated. The entropy maximum change (−ΔS_M) values are 7.40 J kg⁻¹ K⁻¹, 5.6 J kg⁻¹ K⁻¹ and 4.48 J kg⁻¹ K⁻¹, whereas the relative cooling power (RCP) values are 232 J kg⁻¹, 230 J kg⁻¹ and 156 J kg⁻¹ for x = 0.00, 0.05 and 0.10, respectively, under an external field (μ₀H) of 5 T. Through these results, the La_0.6Ba_0.2Sr_0.2Mn_1−xNi_xO₃ (0 ≤ x ≤ 0.1) samples can be suggested for use in magnetic refrigeration technology above room temperature. The electrical resistivity (ρ) vs. temperature plots exhibit a transition from metallic behavior to semiconductor behavior in the vicinity of T_M–SC. The adiabatic small polaron hopping (ASPH) model is applied in the PM-semiconducting part (T > T_MS). Throughout the temperature range, ρ is adjusted by the percolation model. This model is based on the phase segregation of FM-metal clusters and PM-insulating regions.

We present a detailed study on the physical properties of La_0.6Ba_0.2Sr_0.2Mn_1−xNi_xO₃ samples (x = 0.00, 0.05 and 0.1).