Design of a Single-Atom In-N3-S site to Modulate Exciton Behavior in Carbon Nitride for Enhanced Photocatalytic Performance.

Rational tailoring of the local coordination environment of single atoms has demonstrated a significant impact on the electronic state and catalytic performance, but the development of catalysts beyond noble/transition metals is profoundly significant and highly desired. Herein, the main-group metal indium (In) single atom is immobilized on sulfur-doped porous carbon nitride nanosheets (In@CNS) in the form of three nitrogen atoms coordinated with one sulfur atom (In-N3-S). Both theoretical calculations and advanced characterization investigations clearly elucidated that the single-atomic In-N3-S structures on In@CNS are powerful in promoting the dissociation of excitons into more free carriers as well as the charge separation, synergistically elevating electron concentration by 2.19 times with respect to pristine CNS. Meanwhile, the loading of In single atoms on CNS is responsible for altering electronic structure and lowering the Gibbs free energy for hydrogen adsorption. Consequently, the optimized In@CNS-5.0 exhibited remarkable photocatalytic performance, remarkable water-splitting and tetracycline hydrochloride degradation. The H2 production achieved to 10.11 mmol h-1g-1 with a notable apparent quantum yield of 19.70% at 400 nm and remained at 10.40% at 420 nm. These findings open a new perspective for in-depth comprehending the effect of the main-group metal single-atom coordination environment on promoting photocatalytic performance.

Biodegradation of mixed litter-derived dissolved organic matter with varying evenness in a temperate freshwater wetland.

Litter-derived dissolved organic matter (DOM) plays an essential role in biogeochemical cycles. In wetlands, species relative abundance and its change have great influences on input features of litter-derived DOM, including chemical characteristics per se and functional diversity of chemical characteristics. Functional diversity is an important factor controlling organic matter biodegradation, but little is known in terms of the DOM. We mixed litter leachates of four macrophytes with a constant concentration (20 mg DOC L-1) but varying dominant species and volume ratios, i.e. 15:1:1:1 (low-evenness), 5:1:1:1 (mid-evenness), and 2:1:1:1 (high-evenness), generating a gradient of chemical characteristics and functional diversity (represented by functional dispersion index FDis). Based on a 42-d incubation, we measured degradation dynamics of these DOM mixtures, and analyzed potential determinants. After 42 days of incubation, the high-evenness treatments, along with mid-evenness treatments sometimes, had most degradation, while the low-evenness treatments always had least degradation. The degradation of mixtures related significantly to not only the volume-weighted mean chemical characteristics but also FDis. Furthermore, the FDis even explained more variation of degradation. The non-additive mixing effects, synergistic effects (faster degradation than predicted) in particular, on degradation of DOM mixtures were rather common, especially in the high- and mid-evenness treatments. Remarkably, the mixing effects increased linearly with the FDis values (r2adj. = 0.426). This study highlights the critical role of functional diversity in regulating degradation of mixed litter-derived DOM. Resulting changes in chemistry and composition of litter leachates due to plant community succession may exert substantial influences on biogeochemical cycling.

Combined toxicity of erythromycin and roxithromycin and their removal by Chlorella pyrenoidosa.

The ecological effects of antibiotics in surface water have attracted increasing research attention. In this study, we investigated the combined ecotoxicity of erythromycin (ERY) and roxithromycin (ROX) on the microalgae, Chlorella pyrenoidosa, and the removal of ERY and ROX during the exposure. The calculated 96-h median effect concentration (EC50) values of ERY, ROX, and their mixture (2:1 w/w) were 7.37, 3.54, and 7.91 mg∙L-1, respectively. However, the predicted EC50 values of ERY+ROX mixture were 5.42 and 1.51 mg∙L-1, based on the concentration addition and independent action models, respectively. This demonstrated the combined toxicity of ERY+ ROX mixture showed an antagonistic effect on Chlorella pyrenoidosa. During the 14-d culture, low-concentration (EC10) treatments with ERY, ROX, and their mixture caused the growth inhibition rate to decrease during the first 12 d and increase slightly at 14 d. In contrast, high-concentration (EC50) treatments significantly inhibited microalgae growth (p < 0.05). Changes in the total chlorophyll contents, SOD and CAT activities, and MDA contents of microalgae suggested that individual treatments with ERY and ROX induced higher oxidative stress than combined treatments. After the 14-d culture time, residual Ery in low and high concentration Ery treatments were 17.75% and 74.43%, and the residual Rox were 76.54% and 87.99%, but the residuals were 8.03% and 73.53% in ERY+ ROX combined treatment. These indicated that antibiotic removal efficiency was higher in combined treatments than that in individual treatments, especially at low concentrations (EC10). Correlation analysis suggested that there was a significant negative correlation between the antibiotic removal efficiency of C. pyrenoidosa and their SOD activity and MDA content, and the enhanced antibiotic removal ability of microalgae benefited from increased cell growth and chlorophyll content. Findings in this study contribute to predicting ecological risk of coexisting antibiotics in aquatic environment, and to improving biological treatment technology of antibiotics in wastewater.

Structural Evolution of Graphitic Carbon Derived from Ionic Liquids-Dissolved Cellulose and Its Application as Lithium-Ion Battery Anodes.

With an attempt to replace petroleum-derived commercial graphite (CG) with biomass-derived carbon, microcrystalline cellulose (MCC) dissolved in 1-butyl-3-methylimidazolium acetate (BMIMAcO) was facilely carbonized to prepare cellulose-derived carbon under a low-temperature range of 250-1600 °C. TEM and AFM results revealed structural evolution of carbon nanosheets starting from carbon dots. The XRD and Raman results showed that the degree of crystallinity of the MCC-derived carbon was apparently enhanced as the temperature was increased to 93.02% at 1600 °C, while the XPS results revealed that the nitrogen content was greatly reduced with increasing temperature. BMIMAcO not only induced low-temperature graphitization of MCC-derived carbon but also provided nitrogen doping for the carbon. Used as an anode of lithium-ion batteries (LIBs), the carbon synthesized at 750 °C showed the best cyclic stability and reversible capacity (1052.22 mAh g-1 at 0.5 A g-1 after 100 cycles and 1017.46 mAh g-1 at 1 A g-1 after 1000 cycles) compared to other MCC-derived carbon and CG. In addition, the costs of cellulose-derived carbon are much lower than those of the petroleum-derived graphite, showing environmental and economical merits for LIB anode production.

Waste-to-Resource Strategy to Fabricate Functionalized MOFs Composite Material Based on Durian Shell Biomass Carbon Fiber and Fe3O4 for Highly Efficient and Recyclable Dye Adsorption.

Recently, metal-organic frameworks (MOFs), which are porous inorganic-organic hybrid materials consisting of metal ions (clusters or secondary building units) and organic ligands through coordination bonds, have attracted wide attention because of their high surface area, huge ordered porosity, uniform structural cavities, and excellent thermal/chemical stability. In this work, durian shell biomass carbon fiber and Fe3O4 functionalized metal-organic framework composite material (durian shell fiber-Fe3O4-MOF, DFM) was synthesized and employed for the adsorption removal of methylene blue (MB) from wastewater. The morphology, structure, and chemical elements of the DFM material were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), transmission electron microscope (TEM), and X-ray photoelectron spectroscope (XPS) techniques. Adsorption conditions such as pH, adsorption time, and temperature were optimized. The adsorption isotherm and kinetics results show that the adsorption process of DFM material to MB is more in line with the Freundlich model and pseudo-second-order kinetic model. Using these models, the maximum adsorption capacity of 53.31 mg/g was obtained by calculation. In addition, DFM material could be easily reused through an external magnet and the removal rate of MB was still 80% after five adsorption cycles. The obtained results show that DFM composite material, as an economical, environmentally friendly, recyclable new adsorbent, can simply and effectively remove MB from wastewater.

A review for recent advances on soil washing remediation technologies.

Contaminated soils have caused serious harm to human health and the ecological environment due to the high toxicity of organic and inorganic pollutants, which has attracted extensive attention in recent years. Because of its low cost, simple operation and high efficiency, soil washing technology is widely used to permanently remove various pollutants in contaminated soils and is considered to be the most promising remediation technology. This review summarized the recent developments in the field of soil washing technology and discusses the application of conventional washing agents, advanced emerging washing agents, the recycling of washing effluents and the combination of soil washing and other remediation technologies. Overall, the findings provide a comprehensive understanding of soil washing technology and suggest some potential improvements from a scientific and practical point of view.

Potassium hydroxide-modified algae-based biochar for the removal of sulfamethoxazole: Sorption performance and mechanisms.

Biochar has been deemed one of the most promising sorbents for the removal of organic pollutants from aqueous solution. In this study, potassium hydroxide-modified Enteromorpha prolifera biochars (PEBCs) were prepared for the first time and applied for efficient sorption of a typical antibiotic, sulfamethoxazole (SMX). The characteristics of PEBCs, including morphology, pore structure, graphitization degree, surface functional groups, and surface element composition, were investigated. Moreover, sorption kinetic and isotherm experiments were carried out to explore the sorption process, performance, and mechanisms. The maximum sorption capacity for SMX can reach 744 mg g-1, which is much higher than that reported for sorbents. The sorption of SMX onto PEBCs was controlled by both physical and chemical processes. Moreover, pore filling, hydrogen bonding, partitioning, π-π stacking, and electrostatic interactions were possible sorption mechanisms. This study indicated that the structure and properties of algal biochar can be further improved by potassium hydroxide modification at high temperature and applied as an excellent sorbent for the removal of antibiotics from aqueous solution.

Surface Permeability of Membrane and Catalytic Performance Based on Redox-Responsive of Hybrid Hollow Polymeric Microcapsules.

"Smart" polymeric microcapsules with excellent permeability of membranes have drawn considerable attention in scientific and industrial research such as drug delivery carriers, microreactors, and artificial organelles. In this work, hybrid hollow polymeric microcapsules (HPs) containing redox-active gold-sulfide bond were prepared with bovine serum albumin, inorganic metal cluster (AuNCs), and poly(N-isopropylacrylamide) conjugates by using Pickering emulsion method. HPs were transferred from water-in-oil to water-in-water by adding PEGbis(N-succinimidylsuccinate). To achieve redox-responsive membrane, the Au-S bond units incorporated into the microcapsules' membranes, allowed us to explore the effects of a new stimuli, that is, the redox Au-S bond breaking on the microcapsules' membranes. The permeability of these hybrid hollow polymeric microcapsules could be sensitively tuned via adding environment-friendly hydrogen peroxide (H2O2), resulting from a fast fracture of Au-S bond. Meanwhile, AuNCs and conjugates could depart from the microcapsules, and enhance the permeability of the membrane. Based on the excellent permeability of the membrane, phosphatase was encapsuled into HPs and p-nitrophenyl phosphate as a substrate. After adding 1 × 10-2 and 1 × 10-4 M H2O2, the catalytic efficiency was nearly 4.06 and 2.22 times higher than that of HPs in the absence of H2O2, respectively. Hence, the unique redox-responsive HPs have potential applications in biocatalytic reaction, drug delivery, and materials as well as in bioscience.

Genomic analysis of worldwide sheep breeds reveals PDGFD as a major target of fat-tail selection in sheep.

BACKGROUND: Fat tail is a unique trait in sheep acquired during domestication. Several genomic analyses have been conducted in sheep breeds from limited geographic origins to identify the genetic factors underlying this trait. Nevertheless, these studies obtained different candidates. The results of these regional studies were easily biased by the breed structures. RESULTS: To minimize the bias and distinguish the true candidates, we used an extended data set of 968 sheep representing 18 fat-tailed breeds and 14 thin-tailed breeds from around the world, and integrated two statistical tests to detect selection signatures, including Genetic Fixation Index (FST) and difference of derived allele frequency (ΔDAF). The results showed that platelet derived growth factor D (PDGFD) exhibited the highest genetic differentiation between fat- and thin-tailed sheep breeds. Analysis of sequence variation identified that a 6.8-kb region within the first intron of PDGFD is likely the target of positive selection and contains regulatory mutation(s) in fat-tailed sheep. Histological and gene expression analyses demonstrated that PDGFD expression is associated with maturation and hemostasis of adipocytes. Further retrospective analysis of public transcriptomic datasets revealed that PDGFD expression is down-regulated during adipogenesis in both human and mouse, and is higher in fat tissues of obese individuals than that in lean individuals. CONCLUSIONS: These results reveal that PDGFD is the predominant factor for the fat tail phenotype in sheep by contributing to adiopogenesis and maintaining the hemostasis of mature adipocytes. This study provides insights into the selection of fat-tailed sheep and has important application to animal breeding, as well as obesity-related human diseases.

Toluene induces hormetic response of soil alkaline phosphatase and the potential enzyme kinetic mechanism.

Hormesis of soil enzyme that involved in heavy metal has been attracting much more attention for risk assessment of heavy metal toxicity, but insufficient studies were conducted to define the hormetic responses induced by toluene or other organic pollutions. The objectives of this study were to investigate the hormetic responses of soil enzyme induced by toluene and explore the potential enzyme kinetic mechanism. Soil alkaline phosphatase (ALP) activity was regarded as the endpoint to explore the hormetic responses under different doses of toluene (0.0, 0.1, 0.5, 1.0, 2.0, 3.0, 5.0, 10.0, 50.0 and 100.0 µL g-1). Subsequently, we conducted the experiments of enzymatic reaction kinetics and pure enzyme to further verify the potential mechanisms of soil ALP's hormesis. Results showed that ALP activities at 0.1-1.0 µL g-1 toluene were significantly increased in contrast to the control (0 µL g-1 toluene) (P < 0.05) at the exposure time of 30, 36, 48 and 54 h, with the maximum stimulation magnitudes of 24-43%. ALP activities were almost not affected by toluene (2-100 µL L-1) in the whole experimental period (6-54 h). Meanwhile, the values of catalytic efficiency (the radio Vmax/Km, Vmax: maximum reaction velocity and Km: Michaelis constant) and Vmax significantly increased compared with the control, but the value of Km decreased from 2.5 to 1.6. Overall, low dose toluene can induce hormesis of soil ALP. The potential reason is that low-dose toluene could enhance the combination of soil ALP and substrates. We believe that this study will provide a new viewpoint for ecological risk assessment of toluene contaminated soils.

Interactive effects of roxithromycin and freshwater microalgae, Chlorella pyrenoidosa: Toxicity and removal mechanism.

Roxithromycin (ROX) has received increasing concern due to its large usage, ubiquitous detection in environment and high ecotoxicology risk. This study investigated the acute and chronic effects of ROX on the growth, chlorophyll, antioxidant enzymes, and malonaldehyde (MDA) content of Chlorella pyrenoidosa, as well as the removal mechanism of ROX during microalgae cultivation. The calculated 96 h median effective concentration of ROX on yield (EyC50) and specific growth rate (ErC50) of C. pyrenoidosa was 0.81 and 2.87 mg/L, respectively. After 96 h exposure, 1.0 ~ 2.0 mg/L of ROX significantly inhibited the synthesis of chlorophyll and promoted the activities of SOD and CAT (p < 0.05). The MDA content increased with the ROX concentration increasing from 0.5 ~ 1.0 mg/L, and then decreased to 105.76% of the control exposure to 2.0 mg/L ROX, demonstrating the oxidative damage could be moderated by the upregulation of SOD and CAT activities. During the 21 d chronic exposure, low concentration of ROX (0.1 and 0.25 mg/L) showed no significant effect on the growth and chlorophyll content of algae during the first 14 d, but significantly inhibited the growth of algae and the synthesis of chlorophyll at 21 d (p < 0.05 or p < 0.01). 1.0 mg/L ROX significantly inhibited the growth of microalgae during 3 ~ 21 d and the synthesis of chlorophyll at 7 ~ 21 d. High concentration and long-term exposure of low concentration of ROX caused the SOD and CAT activities and MDA content to increase, demonstrating a higher level of oxidative damage of microalgae. During the first 14 d, abiotic removal of ROX played a more important role, contributing about 12.21% ~ 21.37% of ROX removal. After 14 d, the biodegradation of ROX by C. pyrenoidosa gradually became a more important removal mechanism, contributing about 45.99% ~ 53.30% of ROX removal at 21 d. Bio-adsorption and bioaccumulation both played minor roles in the removal of ROX during algae cultivation.

Fate and transfer of heavy metals following repeated biogas slurry application in a rice-wheat crop rotation.

The application of biogas slurry, from anaerobic digestion of livestock excreta, to cropland has proven to be an effective mechanism for recycling nutrients within farms. However, the potential pollution of heavy metals from repeated biogas slurry fertilization has not received much attention. Here we present the results of a field experiment under rice-wheat rotation demonstrating the accumulation, speciation distribution and plant uptake of heavy metals (Cu, Zn, Pb and Cd) in soil following biogas slurry application. The treatments were: zero biogas slurry application (BS0), and biogas slurry application for three (BS3) and five (BS5) years, at a rate of 450 m3 ha-1 y-1. Our findings show that biogas slurry fertilization resulted in accumulation of Cu and Zn in the soil. The concentrations of soil Cu and Zn under BS5 were, respectively, 38 and 29% greater in the wheat season and 35 and 35% greater in the rice season relative to BS0 (p < 0.05). The bioavailability of soil Cu and Zn increased following biogas slurry application. Plant uptake of Cu and Zn to all parts of wheat and rice plants (excluding Cu in wheat straw) increased with the years of biogas slurry application (p < 0.05), and the concentration of Cd in wheat grain was significantly greater in BS5 relative to BS0 (p < 0.05). After five years of biogas slurry fertilization, concentrations of Cu, Zn, Pb and Cd in wheat grains were 3.28, 25.19, 0.11 and 0.053 mg kg-1 and 4.24, 33.78, 0.12 and 0.035 mg kg-1 for rice grains, respectively, all within the safety limits. Our results demonstrate that repeated biogas slurry fertilization for five years has a relatively low pollution risk of heavy metals. However, long-term field monitoring and co-application with metal-immobilizing materials are required to ensure the safety of its application to cropland.

Time-Dependent Hormetic Response of Soil Alkaline Phosphatase Induced by Cd and the Association with Bacterial Community Composition.

Hormetic dose-response that involved Cd in soils is increasingly paid attentions for risk assessment of Cd toxicity, but insufficient studies were conducted to define the temporary modification of soil enzyme and the potential microbial responses. The present study chooses soil alkaline phosphatase (ALP) as endpoint to uncover the time-dependent hormetic responses to low doses of Cd and its association with bacterial community composition. The results showed that addition of 0.01-3.0 mg kg-1 Cd significantly increased ALP's activities with maximum stimulatory magnitude of 11.4-27.2%, indicating a typical hormesis. The response started at 12 h after Cd addition and maintained about 24 h. This demonstrated that the hormetic response is time-dependent and transient. Changes of soil bacterial community composition showed that, at 6 h, relative abundances (RAs) of Proteobacteria and Firmicutes at phylum and Pontibacter, Bacillaceae-Bacillus, Bacillaceae1-Bacillus, and Paenisporosarcina at genus significantly correlated with ALP's activities at 12-36 h (P < 0.05). This suggests that soil bacteria likely showed an earlier response to Cd and potentially contributes to the subsequent soil enzyme's hormesis. In addition, it was found that Gram-negative bacteria other than Gram-positive bacteria are prone to exhibiting a hormetic response under Cd stress. Our findings provide much insight into ecotoxicological risk assessment for soil Cd pollution.

Impact of timing on in-patient outcomes of complete repair of tetralogy of Fallot in infancy: an analysis of the United States National Inpatient 2005-2011 database.

BACKGROUND: This study aimed to investigate whether age at complete repair of tetralogy of Fallot (TOF) impacts postoperative morbidity and length of hospital stay in infants less than 365 days of age. METHODS: The United States Nationwide Inpatient Sample was searched for infants 0-365 days of age that underwent complete repair of TOF between 2005 and 2011. Patients were categorized based on age at time of repair: 0-30 days; 31-90 days; 91-180 days; > 180 days. RESULTS: A total of 1112 infants were included in the study. Multivariate analysis showed the risk of postoperative complications was 40% lower in infants ≥91 days old at the time of repair as compared to those ≤30 days old. In addition, children > 30 days old at the time of repair had a significantly shorter length of hospital stay than those aged ≤30 days. In the subgroup with elective repair, older age was associated with a shorter length of hospital stay as compared to those ≤30 days old at repair, while association between age at complete repair of TOF and postoperative complication was not significant among the groups after adjusting for confounders. CONCLUSIONS: In children < 1 year old, postoperative complications and length of hospital stay are affected by the timing of complete repair of TOF.

Magnitude of the mixture hormetic response of soil alkaline phosphatase can be predicted based on single conditions of Cd and Pb.

In soil ecosystems, it is very challenging to predict mixture hormesis effects. In the present study, soil alkaline phosphatase (ALP) was selected to investigate and predict its potential hormetic responses under Cd and Pb stresses. Typical reverse U-shaped dose-response relationships between ALP activities and the single and combined Cd and Pb were observed, showing a hormetic response of soil itself. The maximum stimulatory magnitudes ranged in 8.0 - 8.6% under 0.004 - 0.2 mg/kg Cd and 80 - 400 mg/kg Pb, respectively. An enhanced stimulation of 15.7% occurred under the binary mixtures of 0.6 mg/kg Cd and 200 mg/kg Pb. In addition, a dosage-independent binary linear regression model was proposed based on an assumption of a linear relationship between the single and combined hormetic responses under Cd and Pb. Our model can well predict ALP's responses in the presence of the two metals' mixtures (p < 0.1). Our findings provided new understandings to hormesis in soil.

Transcriptomics revealed the key molecular mechanisms of ofloxacin-induced hormesis in Chlorella pyrenoidosa at environmentally relevant concentration.

Emerging pollutants such as antibiotics have aroused great concern in recent years. However, the knowledge of low concentration-induced hormesis was not well understood. This study evaluated and quantified hormetic effects of ofloxacin on Chlorella pyrenoidosa. LogNormal model predicted the maximal non-effect concentration was 0.13 mg/L and 2.96 mg/L at 3 and 21 d, respectively. The sensitive alterations in chlorophyll fluorescence suggested PSII was the main target. Transcriptomics revealed ofloxacin inhibited genes related to photosynthetic system while the cyclic electron around PSI decreased the pH value in stroma side and stimulated photoprotection via up-regulating psbS. The stimulation in citrate cycle pathway met the urgent requirements of energy for DNA replication and repair. In addition, the negative feedback of G3P in glycolysis pathway inhibited Calvin cycle. The degradation products illustrated the occurrence of multiple detoxification mechanisms such as demethylation and ring-opening. The mobilization of cytochrome P450 generated the constant detoxication of ofloxacin while glutathione was consumptively involved in biological binding. This study provided new insights into the molecular mechanisms of antibiotic-induced hormesis in microalgae.

Mechanisms of hormetic effects of ofloxacin on Chlorella pyrenoidosa under environmental-relevant concentration and long-term exposure.

Antibiotics are frequently detected in surface water and pose potential threats to organisms in aquatic ecosystem such as microalgae. The occurrence of biphasic dose responses raised the possibility of stimulation of microalgal biomass by antibiotics at environmental-relevant concentration and caused potential ecological risk such as algal bloom. However, the underlying mechanisms of low concentration-induced hormetic effects are not well understood. In this study, we evaluated the hormesis of ofloxacin on Chlorella pyrenoidosa under environmental-relevant concentration and long-term exposure. Results showed the hormetic effects of ofloxacin on cell density and carbon fixation rate (RC). The predicted maximum promotion was 17.45 % by 16.84 µg/L and 20.08 % by 15.78 µg/L at 21 d, respectively. The predicted maximum concentration of non-effect on cell density and RC at 21 d was 3.24 mg/L and 1.44 mg/L, respectively. Ofloxacin induced the mobilization of pigments and antioxidant enzymes to deal with oxidative stress. PCA analysis revealed Chl-a/Chl-b could act as a more sensitive biomarker under acute exposure while chlorophyll fluorescence parameters were in favor of monitoring long-term implication. The hormesis in increased secretion of extracellular organic matters was regarded as a defensive mechanism and accelerated indirect photodegradation of ofloxacin. Bioremoval was dominant and related to biomass accumulation in the total dissipation while abiotic removal appeared slight contributions. This study provided new insights into the understanding of hormesis of microalgae induced by antibiotics.

Impact mechanisms of various surfactants on the biodegradation of phenanthrene in soil: Bioavailability and microbial community responses.

The present study was conducted to systematically explore the mechanisms underlying the impact of various surfactants (CTAB, SDBS, Tween 80 and rhamnolipid) at different doses (10, 100 and 1000 mg/kg) on the biodegradation of a model polycyclic aromatic hydrocarbon (PAH) by indigenous soil microorganisms, focusing on bioavailability and community responses. The cationic surfactant CTAB inhibited the biodegradation of phenanthrene within the whole tested dosage range by decreasing its bioavailability and adversely affecting soil microbial communities. Appropriate doses of SDBS (1000 mg/kg), Tween 80 (100, 1000 mg/kg) and rhamnolipid at all amendment levels promoted the transformation of phenanthrene from the very slow desorption fraction (Fvslow) to bioavailable fractions (rapid and slow desorption fractions, Frapid and Fslow), assessed via Tenax extraction. However, only Tween 80 and rhamnolipid at these doses significantly improved both the rates and extents of phenanthrene biodegradation by 22.1-204.3 and 38.4-76.7 %, respectively, while 1000 mg/kg SDBS had little effect on phenanthrene removal. This was because the inhibitory effects of anionic surfactant SDBS, especially at high doses, on the abundance, diversity and activity of soil microbial communities surpassed the bioavailability enhancement in dominating biodegradation. In contrast, the nonionic surfactant Tween 80 and biosurfactant rhamnolipid enhanced the bioavailability of phenanthrene for degradation and also that to specific degrading bacterial genera, which stimulated their growth and increased the abundance of the related nidA degradation gene. Moreover, they promoted the total microbial/bacterial biomass, community diversity and polyphenol oxidase activity by providing available substrates and nutrients. These findings contribute to the design of suitable surfactant types and dosages for mitigating the environmental risk of PAHs and simultaneously benefiting microbial ecology in soil through bioremediation.

Predicting the bioavailability of polycyclic aromatic hydrocarbons in rhizosphere soil using a new novel in situ solid-phase microextraction technique.

In situ measurement of the bioavailability of organic pollutants in soil is crucial for understanding their environmental behavior and assessing health risks. Due to the high heterogeneity of soil, microscale determination is crucial for achieving high accuracy, but few methods are available. In this study, microsized probes coated with polydimethylsiloxane (PDMS) were used to measure the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in soil in situ. The concentrations of PAHs enriched by the PDMS-coated probes correlated well with the results of bioassays using earthworms (R2 = 0.92-0.99) and ryegrass roots (R2 = 0.92-0.99). Compared with other chemical extraction methods, such as n-butanol extraction, the proposed method has advantages such as in situ operation, microvolume analysis, and negligible interference to the soil environment. In the soil rhizosphere zone, PAHs bioavailability decreased in the following order: rhizosphere > near-rhizosphere > far-rhizosphere. The bioavailability of PAHs in soil amended with biochar was also successfully characterized by the proposed method. Thus, this study developed an in situ and microscale method to predict the bioavailability of organic pollutants in contaminated soils and provides new insight into migration and transformation processes in rhizosphere soil.

Physiological-biochemical responses and transcriptomic analysis reveal the effects and mechanisms of sulfamethoxazole on the carbon fixation function of Chlorella pyrenoidosa.

The occurrence of sulfamethoxazole (SMX) is characterized by low concentration and pseudo-persistence. However, the toxic effects and mechanisms of SMX, especially for low concentration and long-term exposure, are still not clear. This study investigated the effects and mechanisms of SMX on carbon fixation-related biological processes of Chlorella pyrenoidosa at population, physiological-biochemical, and transcriptional levels. Results showed that 1-1000 µg/L SMX significantly inhibited the dry weight and carbon fixation rate of C. pyrenoidosa during 21 d. The upregulation of superoxide dismutase (SOD) and catalase (CAT) activities, as well as the accumulation of malondialdehyde (MDA) demonstrated that SMX posed oxidative damage to C. pyrenoidosa. SMX inhibited the activity of carbonic anhydrase (CA), and consequently stimulated the activity of Rubisco. Principal component analysis (PCA) revealed that SMX concentration was positively correlated with Rubisco and CAT while exposure time was negatively correlated with CA. Transcriptional analysis showed that the synthesis of chlorophyll-a was stabilized by regulating the diversion of protoporphyrin IX and the chlorophyll cycle. Meanwhile, multiple CO2 compensation mechanisms, including photorespiratory, C4-like CO2 compensation and purine metabolism pathways were triggered in response to the CO2 requirements of Rubisco. This study provides a scientific basis for the comprehensive assessment of the ecological risk of SMX.