Catabolism of phenolics from grape peel and its effects on gut microbiota during in vitro colonic fermentation.

BACKGROUND: Grape peels, the main by-products of wine processing, are rich in bioactive ingredients of phenolics, including proanthocyanidins, flavonoids and anthocyanins. Phenolics have the function of regulating intestinal microbiota and promoting intestinal health. From the perspective of the dietary nutrition of grape peel phenolics (GPP), the present study aimed to investigate the influence of GPP on the composition and metabolism of human gut microbiota during in vitro fermentation. RESULTS: The results indicated that GPP could decrease pH and promote the production of short-chain fatty acids. ACE and Chao1 indices in GPP group were lower than that of the Blank group. GPP enhanced the levels of Lachnospiraceae UCG-004, Bacteroidetes and Roseburia, but reduced the Firmicutes/Bacteroidetes ratio. Kyoto Encyclopedia of Proteins and Genome enrichment pathways related to phenolic acid metabolism mainly included flavonoid, anthocyanin, flavone and flavonol biosynthesis. Gut microbiota could accelerate the release and breakdown of phenolic compounds, resulting in a decrease in the content of hesperetin-7-O-glucoside, delphinidin-3-O-glucoside and cyanidin-3-rutinoside etc. In vitro antibacterial test found that GPP increased the diameters of the inhibition zones of Escherichia coli and Staphylococcus aureus in a dose-dependent manner. CONCLUSION: The results of the present study revealed that GPP might be a potential prebiotic-like to prevent diseases by improving gut health. The findings could provide a theoretical basis for the potential to exploit GPP as dietary nutrition to maintain intestinal function. © 2024 Society of Chemical Industry.

The mechanisms of ·OH formation in MnO2 and oxalate system: Implication for ATZ removal.

Manganese oxides (MnO2) are commonly prevalent in groundwater, sediment and soil. In this study, we found that oxalate (H2C2O4) dissolved MnO2, leading to the formation of Mn(II)/(III), CO2(aq) and reactive oxygen species (·CO2-/O2·-/H2O2/·OH). Notably, CO2(aq) played a crucial role in ·OH formation, contributing to the degradation of atrazine (ATZ). To elucidate underneath mechanisms, a series of reactions with different gas-liquid ratios (GLR) were conducted. At the GLR of 0.3, 3.76, and + ∞ 79.4 %, 5.32 %, and 5.28 % of ATZ were eliminated, in which the cumulative ·OH concentration was 39.6 µM, 8.11 µM, and 7.39 µM and the cumulative CO2(aq) concentration was 11.2 mM, 4.7 mM, and 2.8 mM, respectively. The proposed reaction pathway was that CO2(aq) participated in the formation of a ternary complex [C2O4-Mn(II)-HCO4·3 H2O]-, which converted to a transition state (TS) as [C2O4-Mn(II)-CO3-OH·3 H2O]-, then decomposed to a complex radical [C2O4-Mn(II)-CO3·3 H2O]·- and ·OH after electron transfer within TS. It was novel to discover the role of CO2(aq) for ·OH yielding during MnO2 dissolution by H2C2O4. This finding helps revealing the overlooked processes that CO2(aq) influenced the fate of ATZ or other organic compounds in environment and providing us ideas for new technique development in contaminant remediation. ENVIRONMENTAL IMPLICATION: Manganese oxides and oxalate are common in soil, sediment and water. Their interactions could induce the formation of Mn(II)/(III), CO2(aq) and ·CO2-/O2·-/H2O2. This study found that atrazine could be effectively removed due to ·OH radicals under condition of high CO2(aq) concentration. The concentrations of Mn (0.0002-8.34 mg·L-1) and CO2(aq) (15-40 mg·L-1) were high in groundwater, and the surface water or rainfall seeps into groundwater and bring organic acids, which might promote the ·OH formation. The results might explain the missing steps of herbicides transformation in these environments and be helpful in developing new techniques in remediation in future.

Roles of Natural Phenolic Compounds in Polycyclic Aromatic Hydrocarbons Abiotic Attenuation at Soil-Air Interfaces through Oxidative Coupling Reactions.

Little information is available on the roles of natural phenolic compounds in polycyclic aromatic hydrocarbons (PAHs) attenuation at dry soil-air interfaces. The purpose of this study was to determine the roles of model phenolic constituents of soil organic matter (SOM) on the abiotic attenuation of PAHs. The phenolic compounds can significantly change the attenuation rates of PAHs, among which hydroquinone was the most effective in promoting anthracene and benzo[a]anthracene attenuation. Product identification and sequential extraction experiments revealed hydroquinone enhanced the formation of oxidative coupling products and promoted the incorporation of PAHs into humic analogues, thereby reducing potential risks to humans and ecosystems. Electron paramagnetic resonance spectroscopy analyses showed both PAHs and phenolic compounds could donate electrons to Lewis acid sites of soil minerals, resulting in the generation of persistent free radicals (PFRs). PFRs could promote the generation of ·OH to enhance PAH oxidation and could cross-couple with PAHs, resulting in high-molecular-weight oxidative coupling products. This study revealed for the first time the reaction mechanism between PAHs and phenolic components of SOM under relatively dry conditions and provided new insights into promoting PAHs detoxification in soils but also a potential strategy to increase the organic carbon sequestration.

A novel method of rapid detection for heavy metal copper ion via a specific copper chelator bathocuproinedisulfonic acid disodium salt.

The extensive usage and production of copper may lead to toxic effects in organisms due to its accumulation in the environment. Traditional methods for copper detection are time consuming and infeasible for field usage. It is necessary to discover a real-time, rapid and economical method for detecting copper to ensure human health and environmental safety. Here we developed a colorimetric paper strip method and optimized spectrum method for rapid detection of copper ion based on the specific copper chelator bathocuproinedisulfonic acid disodium salt (BCS). Both biological assays and chemical methods verified the specificity of BCS for copper. The optimized reaction conditions were 50 mM Tris-HCl pH 7.4, 200 µM BCS, 1 mM ascorbate and less than 50 µM copper. The detection limit of the copper paper strip test was 0.5 mg/L by direct visual observation and the detection time was less than 1 min. The detection results of grape, peach, apple, spinach and cabbage by the optimized spectrum method were 0.91 µg/g, 0.87 µg/g, 0.19 µg/g, 1.37 µg/g and 0.39 µg/g, respectively. The paper strip assays showed that the copper contents of grape, peach, apple, spinach and cabbage were 0.8 mg/L, 0.9 mg/L, 0.2 mg/L, 1.3 mg/L and 0.5 mg/L, respectively. These results correlated well with those determined by inductively coupled plasma-mass spectrometry (ICP-MS). The visual detection limit of the paper strip based on Cu-BCS-AgNPs was 0.06 mg/L. Our study demonstrates the potential for on-site, rapid and cost-effective copper monitoring of foods and the environment.

Mechanism of nitro-byproducts formation during persulfate-based electrokinetic in situ oxidation for remediation of anthracene contaminated soil.

Persulfate-based electrokinetic (EK) chemical oxidation appears to be a novel and viable strategy for the in situ remediation of polycyclic aromatic hydrocarbons (PAHs) polluted soil; however, the possible toxic byproducts of PAHs have been overlooked. In this study, we systematically investigated the formation mechanism of the nitro-byproducts of anthracene (ANT) during the EK process. Electrochemical experiments revealed that NH4+ and NO2- originating from nitrate electrolyte or soil substrates were oxidized to NO2• and NO• in the presence of SO4•-. Liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS/MS) analysis with 15N labeling revealed the formation of nitro-byproducts (14 kinds), including 1-hydroxy-4-nitro-anthraquinone and its similar derivatives, 4-nitrophenol, and 2,4-dinitrophenol. The nitration pathways of ANT have been proposed and described, mainly including the formation of hydroxyl-anthraquinone-oxygen and phenoxy radicals and the subsequent addition of NO2• and NO•. ANT-based formation of nitro-byproducts during EK, which is usually underestimated, should be further investigated due to their enhanced acute toxicity, mutagenic effects, and potential threat to the ecosystem.

Effect of mulberry leaf or mulberry leaf extract on glycemic traits: a systematic review and meta-analysis.

Mulberry leaf (ML) and mulberry leaf extract (MLE) have numerous biological properties, such as regulating sugar and lipid metabolism, reducing blood glucose, and increasing insulin secretion. The aim of this study was to perform a systematic review and meta-analysis of randomized clinical trials to examine the effect of ML/MLE supplementation on glycemic traits in adults, including fasting blood glucose (FBG), glycosylated hemoglobin (HbA1c), and fasting plasma insulin (FPI). Twelve clinical trials (615 participants) fulfilled the eligibility criteria for the present meta-analysis, which included sensitivity analysis and GRADE (grading of recommendations assessment, development, and evaluation) certainty. Based on the heterogeneity between included studies, a random effects model was applied in the meta-analysis, and the results are expressed as WMD (weighted mean differences) with 95% CI (confidence intervals). Meta-analysis showed that ML/MLE supplementation resulted in a significant reduction in FBG by -0.47 mmol L-1, HbA1c by -2.92 mmol mol-1, and FPI by -0.58 µIU mL-1. In addition, subgroup analysis indicated that long-term supplementation of ML/MLE (≥8 weeks) was more effective for regulation of the glycemic traits in the non-healthy and baseline FPG >6.1 mmol L-1 subgroups. Glycemic regulation by ML/MLE may be attributed to the phytochemicals they contain, which are mainly 1-deoxynojirimycin, flavonoids, phenolics, and polysaccharides.

Aging Characteristics and Ecological Effects of Primary Microplastics in Cosmetic Products Under Different Aging Processes.

Microplastics are becoming an increasingly environmental concern, but only a few studies have focused on primary microplastics. Herein, four primary microplastics (Lapis, Jade, Topaz and White) commonly used in cosmetic products were selected to investigate the effects of sunlight, seawater, and soil aging on their environmental behaviors. After sunlight and seawater aging, the surfaces of all four microplastics developed breaks and cracks, with particle sizes decreased and specific surface areas increased. Topaz exhibited the most significant changes under sunlight and seawater aging and its maximum adsorption capacity of phenanthrene significantly increased by 22.50% and 47.86%, respectively. Under soil aging, amending with either White or Topaz changed the soil bacterial community composition and diversity, but they had less ecological impacts than polyvinyl chloride plastic. The results of this study provide vital information for understanding the aging characteristics, environmental behavior, and ecological effects of primary microplastics under natural aging processes.

Reagent-free electrokinetic remediation coupled with anode oxidation for the treatment of phenanthrene polluted soil.

Electrokinetic in-situ chemical oxidation (EK-ISCO) has attracted much attention during remediation of organic contaminated soil. Oxidants in EK-ISCO brings high cost and negative effects on soil physicochemical properties. In this study, a novel approach of combined electrokinetic treatment and anode oxidation was investigated to remediate phenanthrene polluted soils without adding oxidants. The fabricated Ti4O7 acted as anode, and could generate •OH at the rate of 9.31 × 10-7 mol h-1 at current 5.10 mA cm-2 through direct H2O electrolysis. Electro-osmotic flow (EOF) was used to transport phenanthrene to anode for the subsequent degradation. Sandy soil, fluvo-aquic soil and red soil were selected as typical soil samples, because pH and buffer capacity were two important factors affecting the direction of EOF. Strategies were developed to regulate the direction of EOF, including adding CEM membrane, maintaining soil pH at 3.5-4.0 and mixing solution from anode and cathode chambers. After treatment, more than 81.9% of phenanthrene was removed without adding any oxidants, and the remediated soil had low toxicity for Lolium perenne growth based on 3-d cultivation results. The results indicated that EK-AO had the advantage of less energy consumption and superior environmental friendliness than traditional EK-ISCO.

Oxytetracycline induced the redox of iron and promoted the oxidation of As(III).

Antibiotics and arsenic are two frequently detected contaminants in soils and waters, both of which have potential threats to human health. There are few studies focusing on the interaction between these two groups of contaminants in the environment. In this study, we found that the presence of oxytetracycline could significantly promote the oxidation of inorganic As(III) to As(V) with trace Fe(III) (10 µM) and H2O2 (100 µM) at near natural pH, and OTC was degraded simultaneously. The most possible mechanism was that OTC could complex with Fe(III) and reduce Fe(III) to Fe(II), which further induced the Fenton-like reaction. Furthermore, structural Fe(III) of α-FeOOH and adsorbed Fe(III) of montmorillonite could also induce these reactions, and the oxidation rate of As(III) was higher with Fe(III)-montmorillonite than aqueous Fe(III). Based on this study, the transformation of As(III) and OTC could occur in four natural water samples, including river water, groundwater and livestock wastewaters. The results of this study revealed the overlooked effect of residual tetracyclines antibiotics on the transformation of co-existing As(III) in natural waters and soils, which might greatly reduce the toxicity of As(III) in the environment.

A novel electrokinetic remediation with in-situ generation of H2O2 for soil PAHs removal.

Electrokinetic-Fenton (EK-Fenton) technology requires a high dose of H2O2 to produce •OH radicals, which adds a high cost to the remediation process and raises safety concerns during transportation and storage of H2O2. Moreover, the remediation efficiency of the conventional EK-Fenton process is low due to the meaningless consumption of H2O2 on the electrodes and the alkaline environment near the cathode. In this work, a modified CMK3-gas diffusion electrode (CMK3-GDE) is fabricated. This cathode can continuously generate H2O2, and the cumulative H2O2 concentration can reach 0.23 M during 10 days of the test. The utilization of cation exchange membranes (CEMs) efficiently restricts the decomposition of H2O2 on the electrodes and prevents the alkalization of the soil near the cathode, resulting in a 13.7-43.2% increase of the removal efficiency of polycyclic aromatic hydrocarbons (PAHs). In this new treatment process, PAHs are mainly oxidized into quinones, ketones, alcohols, and small molecule acids, and all these products have lower toxicities than PAHs. The EK-Fenton/CMK3-GDE-CEM system exhibits excellent remediation efficiency for treating PAHs polluted soil, which could be a sustainable, eco-friendly, and low-cost strategy for soil remediation.

Two transformation pathways of Acetaminophen with Fe3+ saturated clay particles in dark or light.

Acetaminophen (AP) has been frequently detected in different environments due to its wide usage as a common analgesic and antipyretic pharmaceutical. Excess residual of AP in the environment may cause biological risk. However, information about its environmental behaviors was limited, especially the interactions with clay minerals. In this study, AP transformation mediated by Fe3+ saturated clay particles was systematically investigated. The results showed 47.6 ± 1.1% or 78.9 ± 0.5% of AP was removed in the presence of Fe3+-montmorillonite respectively in dark or under simulated sunlight irradiation after 10 h. The hypothesized mechanism was that exchangeable ferric ions can either obtain electron from AP to form AP radical, or produce •OH under light, which can further react with AP. In dark condition, AP radicals could cross-couple with each other to form dimers, while oxidation products were also detected under light irradiation due to •OH attacking. Moreover, higher concentration of dissolved oxygen (DO) facilitated Fe3+ regeneration on clay surfaces and more reactive Fe species distributed in lower pH, which could significantly enhance the removal of AP both in dark and light. Results of this study revealed that clay minerals played important roles in the abiotic transformation of AP either in dark or under light irradiation, and oligomerization other than mineralization were the dominant processes.

Persistent Free Radicals from Low-Molecular-Weight Organic Compounds Enhance Cross-Coupling Reactions and Toxicity of Anthracene on Amorphous Silica Surfaces under Light.

Polycyclic aromatic hydrocarbon (PAH) contamination has raised great environmental concerns, while the effects of low-molecular-weight organic compounds (LMWOCs) on PAH photodegradation at amorphous silica (AS)/air interfaces have been largely ignored. In this study, the phototransformation of anthracene (ANT) at amorphous silica (AS)/air interfaces was investigated with the addition of LMWOCs. ANT removal was attributed to •OH attacking and the energy transfer process via 3ANT*. Light irradiation induced the fractured ≡SiO• or ≡Si• generation on AS surfaces, which could react with absorbed H2O and O2 to generate •OH and further yield a series of hydroxylated products of ANT. The presence of citric acid and oxalic acid improved •OH generation and enhanced ANT removal by 1.0- and 2.2-fold, respectively. For comparison, the presence of catechol and hydroquinone significantly decreased ANT removal and produced coupling products. The results of density functional theory calculations suggest that persistent free radicals (PFRs) on AS surfaces from catechol or hydroquinone after •OH attacking prefer to cross-couple with ANT via C-C bonding rather than self-couple. Dianthrone and cross-coupling products might possess higher ecotoxicity, while hydroxylated products were less ecotoxic than their parent compounds based on Ecological Structure Activity Relationships (ECOSAR) estimation. The results of this study revealed the potential ecotoxicity of PAH-adsorbed particulates coexisting with LMWOCs and also provided a new insight into PAH transformation through PFR pathways.

Nano Fe2O3 embedded in montmorillonite with citric acid enhanced photocatalytic activity of nanoparticles towards diethyl phthalate.

Nano-Fe2O3 embedded in montmorillonite particles (Fe-Mt) were prepared to degrade diethyl phthalate (DEP) with citric acid (CA) under xenon light irradiation. Compared to pristine montmorillonite (Na-Mt), the embedding process increased 14.5-fold of iron content and 1.8-fold of specific surface area. The synthesized Fe-Mt have more oxygen vacancies than Fe2O3 nanoparticles (nFe2O3), which could induce more reactive oxygen species (ROSs) generation in the presence of CA under xenon lamp irradiation. Fe-Mt with CA enhanced photo-assisted degradation of DEP 2.5 times as compared to nFe2O3 with CA. Quenching experiments, electron paramagnetic resonance (EPR) spectroscopy and identification of products confirmed that surface-bound •OH was the main radical to degrade DEP. Common anions (i.e., NO3-, CO32-, Cl-) and humic acid could compete •OH with DEP and cause slower degradation of DEP. The removal efficiency of DEP was more than 56% with Fe-Mt after three recycles, and the dissolved Fe concentration from Fe-Mt was below 75 µmol/L, indicating Fe-Mt had a good stability as a catalyst. Fe-Mt together with CA appeared to be a promising strategy to remove organic pollutants in surface water, or topsoil under solar irradiation.

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The migration and settlement of oyster larvae significantly affect the distribution, recruitment, establishment and ecological services of oyster populations. We investigated the variations of Crassostrea sikamea larvae abundances between the two water layers and between the two experimental sites (seed bed and spawning bed) in Xiangshan Bay within a tidal cycle (9 sampling times), and explored the spatial patterns in larval settlement and spat growth at three intertidal zones (top, T; middle, M and bottom, B) of both experimental sites by a field settlement experiment. At the seed bed and spawning bed, oyster larvae abundance at the surface water significantly changed with sampling time. At the seed bed, oyster larvae abundance (20.8±5.6 larvae·L-1) was greatest at the high flood tide, and was significantly greater than that at the other eight sampling times. Contrasting results were found at the spawning bed where oyster larvae abundance was the lowest (0.1±0.1 larvae·L-1) at the high flood tide. At each site, oyster larvae abundance at the bottom water did not change within the tidal cycle. At the seed bed, total abundance, survival rate and shell height of the settled oysters significantly varied across intertidal zones, ranking as B>T=M for total oyster abundance, and T>M>B for survival rate and shell height. There was no significant difference in live spat abundance among intertidal zones. At the spawning bed, the total and live abundances, survival rate and shell height of the settled oysters had no difference among intertidal zones. Our results indicate that oyster larvae commonly settle at the high flood tide, and the abundance of settled spats are similar between seed bed and spawning bed.

The formation of •OH with Fe-bearing smectite clays and low-molecular-weight thiols: Implication of As(III) removal.

Low-molecular-weight thiols (LMWTs) are widely occurring in waters and soils, which can act as electron shuttles in biogeochemical cycles. It is interesting to study the interactions between LMWTs and clay minerals, which would produce free radicals on clay surfaces and influence As(III) transformation. Batch experiments and spectroscopic analysis in combined with computational modeling were conducted with three Fe-bearing clay minerals (Na-NAu-1, Na-NAu-2 and Na-SAz-2) and four LMWTs (l-cysteine, cysteamine, homocysteine, and glutathione) to investigate the reaction mechanisms of LMWTs with Fe-bearing clay minerals and influences of clay types and LMWT structures on the interactions. The results showed that Fe-bearing clay minerals can improve 2.4-3.7 times of •OH formation in 96-h LMWTs oxidation. Quenching experiments confirmed surface-Fenton-like reactions were the main pathways of •OH formation in the presence of Fe-bearing smectite clay minerals. The most possible hypothesis is that structural Fe (III) can accept electrons from LMWTs through proton-coupled transfer from -SH functional group, which was supported by FTIR, XRD and Mössbauer spectroscopies. The results of DFT calculations suggested that clay surfaces could accelerate RS• formation and stabilize the radicals. The addition of Na-NAu-2 in the cystein solution could increase As(III) oxidation to As(V) from 16.3% to 42.0%. The results imply that in-situ •OH formation in the presence of LMWTs and smectite clays may be an important geochemical process for the transformation of environmental contaminants.

Transformation of tetracyclines induced by Fe(III)-bearing smectite clays under anoxic dark conditions.

Smectite clays are widely found in subsurface soils and waters. Although they strongly sequester tetracyclines (TCs), little is known about their reactions with these antibiotics under dark anoxic conditions. This study investigated the interactions between TCs and Fe-bearing smectite clays and the influences of environmental factors. Fe-bearing smectite clays were shown to significantly induce the transformation of TCs, including tautomerization, dechlorination, and dehydration. Moreover, the adsorbed TCs reduced the structural Fe(III) in clay particles to structural Fe(II) through electron transfer. The transformation of TCs was more readily induced by smectite clays with a higher rather than a lower Fe content. Tetrahedral Fe(III), and distorted cis- or trans-octahedral Fe(III), were more reactive as an electron acceptor than cis-octahedral Fe(III), as observed on the Mössbauer and FTIR spectra. A lower pH facilitated the adsorption of TCs through dimethyl-amino, amide, and conjugated -OH functional groups and induced a higher rate of TCs transformation. The transformation of chlortetracycline (CTC) was faster than that of oxytetracycline or tetracycline (TTC) due to -Cl substitution. The major transformation CTC products included keto-CTC, epi-CTC, iso-CTC, anhydro-CTC and TTC. Mixtures of these transformed products were found to have a higher acute toxicity than their parent compounds to Photobacterium phosphoreum T3. Our study revealed several previously overlooked interactions between TCs and clay particles that could cause these antibiotics to become unstable in the subsurface environment, with negative effects on the soil-borne microbial community.

Effects of alkali-treated agricultural residues on nitrate removal and N2O reduction of denitrification in unsaturated soil.

Lignocellulosic agricultural residues were utilized as denitrification carbon substrates to improve the purification capacity of unsaturated soil and alleviate nitrate pollution of groundwater. In this study, corncob and wheat straw were treated by calcium hydroxide to improve biodegradability and enhance denitrification potential. Calcium hydroxide treatment decreased the contents of lignin (i.e., from 16.7 wt% to 15.2 wt% in corncob and from 21.9 wt% to 20.6 wt% in wheat straw), increased potential biodegradable carbon by 4.4-5.3 times, reached complete nitrate removal 7-14 days earlier and decreased N2O/(N2O+N2) ratios by 85-99%. The results provide an insight into the application of alkali-treated agricultural residues as denitrification carbon sources to alleviate nitrate transport to groundwater and reduce potential greenhouse effect.

Selective enhancement and verification of woody biomass digestibility as a denitrification carbon source.

The denitrification efficiency of woody biomass as carbon source is low because of its poor carbon availability. In this study, representative poplar sawdust was pretreated with lime and peracetic acid to enhance the biomass digestibility to different degrees; sawdust was then mixed with soil to investigate its denitrification efficiency. Under controllable conditions (25-95°C, 12-24h, varying dosages), sawdust digestibility (characterized by reducing sugar yield) was selectively enhanced 1.0-21.8 times over that of the raw sawdust (28.8mgeq.glucoseg-1 dry biomass). This increase was mainly attributed to the removal of lignin from the biomass. As a carbon source, the sawdust (digestibility enhanced by 5.4 times) increased the nitrate removal rate by 4.7 times, without N2O emission. However, the sawdust with high digestibility (12.6 or 18.0 times), despite releasing more dissolved organic carbon (DOC), did not exhibit further increase in denitrification efficiency, and emitted N2O.