Five-year warming does not change soil organic carbon stock but alters its chemical composition in an alpine peatland

Climate warming may promote soil organic carbon(SOC)decomposition and alter SOC stocks in terrestrial ecosystems,which would in turn affect climate warming.We manipulated a warming experiment using open-top chambers to investigate the effect of warming on SOC stock and chemical composition in an alpine peatland in Zoigêon the eastern Tibetan Plateau,China.Results showed that 5 years of warming soil temperatures enhanced ecosystem respiration during the growing season,promoted above-and belowground plant biomass,but did not alter the SOC stock.However,labile O-alkyl C and relatively recalcitrant aromatic C contents decreased,and alkyl C content increased.Warming also increased the amount of SOC stored in the silt-clay fraction(<0.053 mm),but this was offset by warming-induced decreases in the SOC stored within micro-and macroaggregates(0.053–0.25 and>0.25 mm,respectively).These changes in labile and recalcitrant C were largely associated with warming-induced increases in soil microbial biomass C,fungal diversity,enzyme activity,and functional gene abundance related to the decomposition of labile and recalcitrant C compounds.The warming-induced accumulation of SOC stored in the silt-clay fraction could increase SOC persistence in alpine peatland ecosystems.Our findings suggest that mechanisms mediated by soil microbes account for the changes in SOC chemical composition and SOC in different aggregate size fractions,which is of great significance when evaluating SOC stability under climate warming conditions.

Enhanced hydrolytic removal of tylosin in wastewater using polymer-based solid acid catalysts converted from polystyrene

Antibiotic production wastewater usually contains high concentrations of antibiotic residues,which can cause instability and deterioration of biological wastewater treatment units and also domestication and proliferation of antibiotic-resistance bacteria.An effective pretreatment on antibiotics production wastewater is expected to selectively reduce the concentration of antibiotics and decrease the toxicity,rather than mitigate organic and other contaminants before further treatments.In this work,two polymer-based solid acids,PS-S and CPS-S bearing high concentrations of-SOH_(3)groups (up to 4.57 mmol/g),were prepared and successfully used for hydrolytic mitigation of 100 mg/L tylosin within 20 min.The co-existence of high concentrations of COD and humic substances did not affect the mitigation of tylosin obviously,while more than 500 mg/L of nitrogenous compounds suppressed the hydrolytic efficiency.Recycle and reuse experiments showed that the solid acids performed well in five cycles after regeneration.Three transformation products (P1,P2 and P3)were identified using UPLC-QTOF-MS/MS.Sugar moieties including mycarse,mycaminose,and mycinose detached and released simultaneously or in order from the 16-member lactone ring through desugarization,which led to a dramatic decrease in antibacterial activity as revealed by cytotoxicity evaluations using S.aureus.Ecotoxicity estimation indicated the acute toxicities of the hydrolyzed products to model species (e.g.,fish,daphnid and green algae) were classified as“not harmful”.This work suggested an effective and selective method to pretreat tylosin-contained production wastewater by using polymer-based solid acids.These results will shed light on effective elimination of antibiotics pollution from pharmaceutical industries through strengthening the pretreatments.

Conversion of biochar into sulfonate-bearing solid acids used for the hydrolysis of tylosin:the effect of aromaticity and degree of condensation

In the last few decades,sulfonated carbon materials have garnered significant attention as Brøsted solid acid catalysts.The sulfonation process and catalytic activity of sulfonated biochar can be influenced by the aromaticity and degree of condensation exhibited by biochar.However,the relationships between the aromaticity,sulfonating ability,and resultant catalytic activity are not fully understood.In this study,biochar samples pyrolyzed at 300-650℃ exhibiting different aromaticity and degrees of condensation were sulfonated and employed as sulfonate-bearing solid catalysts for hydrolytically removing tylosin.They exhibited excellent hydrolytic performance and their kinetic constants were positively correlated with the total acidity and negatively correlated with their aromaticity.This study has uncovered the relationship between the structure,properties,sulfonating ability,and subsequent hydrolytic performance of biochar samples.It was observed that the aromaticity of biochar decreased as the pyrolysis temperature increased.Lower pyrolysis temperatures resulted in a reduced degree of condensation,smaller ring size,and an increased number of ring edge sites available for sulfonation,ultimately leading to enhanced catalytic performance.These findings provide valuable insights into the fundamental chemistry behind sulfonation upgrading of biochar,with the aim of developing functional catalysts for mitigating antibiotics in contaminated water.

Conversion of carbonaceous materials into solid acids for tylosin mitigation:effect of preprocessing methods on the reactivity of sulfonation reaction

Carbon-based solid acids have been successfully employed as acidic catalysts for pollutant mitigation in wastewater.To fully tap the potentials of commercially viable carbons for the preparation of solid acids and enhance their catalytic performances is a challenging problem.In this work,three commercialized carbons including biochar,activated carbon and graphite were preprocessed(ball-milling,Hummer exfoliation,HNO3 soaking,and microwave heating in HNO_(3),etc.),sulfonated,and evaluated as solid-acid catalysts for tylosin mitigation.Graphite-originated solid acid performed the best through a balling-milling preprocess,while biochar-originated solid acids behaved well under all preprocessing treatments,in which 40 mg L^(−1) of tylosin was mitigated within 8 min by 1 g L^(−1) of biochar-originated solid acids.The biochar solid acid through the ball-milling preprocess presented high total acidity and large amounts of-SO_(3)H groups,due to dramatically increased surface area and the rise of activation groups(hydroxyl,alkyl and alkoxy groups,etc.)facilitating electrophilic reaction.In addition,decreased particle size and aromaticity and increased structural defects also contributed.Theoretical calculation of average local ionization energy(ALIE)of condensed aromatic model molecules with substituted activation groups confirmed the promoting effects on sulfonation from strong to weak were 8.40-9.06 eV.These findings have deepened the knowledge in tuning carbon surface chemistry for better sulfonation,thus strengthening catalytic degradation of tylosin.The value of this study is in pulling a clear thread for maneuvering solid-acid catalysts using carbons,which holds a novel promise for rationally functionalizing biochar-based catalysts for the remediation of macrolide antibiotics in polluted water.

Brilliant red X-3B uptake by a novel polycyclodextrin-modified magnetic cationic hydrogel:Performance,kinetics and mechanism

A novel polycyclodextrin-modified magnetic cationic hydrogel(PCD-MCH) was developed and its performance,kinetics and mechanism for the removal of reactive brilliant red X-3B(X-3B) were studied.The results showed that the zeta-potential of PCD-MCH was 32.8 to16.7 mV at pH 3.0-10.5.The maximum X-3B adsorption capacity of PCD-MCH was2792.3 mg/g.The adsorption kinetics could be well-described by the Weber-Morris model and the homogeneous surface diffusion model(HSDM).Diffusion stages corresponding to surface or film diffusion,intra-particle or wide mesopore diffusion,and narrow mesopore/micropore diffusion occurred at 0-120,120-480 and 480-1200 min,respectively.The latter two diffusion stages were rate-controlling for X-3B adsorption kinetics.At the initial X-3B concentration of 600 mg/L,the diffusion coefficient(Ds) and external mass transfer coefficient in the liquid phase(kF) were 3x10^-11 cm^2/min and 4.68 x 10^-6 cm/min,respectively.X-3B approaching the center of PCD-MCH particles could be observed at 360 min.At the end of the third diffusion stage,the Cp at q/qe=0 was 45.20 mg/L,which was close to the homogeneous Cp value of 46 mg/L along the radius of PCD-MCH particles.At pH 3.0-10.0,PCD-MCH showed stable X-3B adsorption capacities.After five regeneration-reuse cycles,the residual adsorption capacity of regenerated PCD-MCH was higher than 892.7 mg/g.The corresponding adsorption mechanism was identified as involving electrostatic interactions,cyclodextrin cavities and hydrogen bonds,of which cyclodextrin cavities showed prominent capture performance towards dye molecules through the formation of inclusion complexes.

Nitrate removal from aqueous solutions by magnetic cationic hydrogel:Effect of electrostatic adsorption and mechanism

Excessive nitrate(NO3-)is among the most problematic surface water and groundwater pollutants.In this study,a type of magnetic cationic hydrogel(MCH)is employed for NO3-adsorption and well characterized herein.Its adsorption capacity is considerably pHdependent and achieves the optimal adsorption(maximum NO3--adsorption capacity is95.88±1.24 mg/g)when the pH level is 5.2-8.8.The fitting result using the homogeneous surface diffusion model indicates that the surface/film diffusion controls the adsorption rate,and NO3-approaches the center of MCH particles within 30 min.The diffusion coefficient(Ds)and external mass transfer coefficient(kF)in the liquid phase are1.15×10-6 cm2/min and 4.5×10-6 cm/min,respectively.The MCH is employed to treat surface water that contains 10 mg/L of NO3-,and it is found that the optimal magnetic separation time is 1.6 min.The high-efficiency mass transfer and magnetic separation of MCH during the adsorption-regeneration process favors its application in surface water treatment.Furthermore,the study of the mechanism involved reveals that both-N+(CH3)3 groups and NO3-are convoluted in adsorption via electrostatic interactions.It is further found that ion exchange between NO3-and chlorine occurs.