Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin f...Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin first”strategy,corn straw is converted to valuable chemicals including lignin monomers,furfural and 5-methoxymethylfurfural via a two steps process.The key of this research lies in the development of a green and low-cost catalytic process utilizing magnetic Raney Ni catalyst and high boiling point ethylene glycol.The utilization of neat ethylene glycol as the sole slovent under atmospheric conditions obviates the need for additional additives,thereby facilitating the entire process to be conducted in glass flasks and rendering it highly convenient for scaling up.In the initial step,depolymerization of corn straw lignin resulted in a monomer yield of 18.1 wt%.Subsequently,in a dimethyl carbonate system,the carbohydrate component underwent complete conversion in a one-pot process,yielding furfural and 5-methoxymethylfurfural as the primary products with an impressive yield of 47.7%.展开更多
Prediction of production decline and evaluation of the adsorbed/free gas ratio are critical for determining the lifespan and production status of shale gas wells.Traditional production prediction methods have some sho...Prediction of production decline and evaluation of the adsorbed/free gas ratio are critical for determining the lifespan and production status of shale gas wells.Traditional production prediction methods have some shortcomings because of the low permeability and tightness of shale,complex gas flow behavior of multi-scale gas transport regions and multiple gas transport mechanism superpositions,and complex and variable production regimes of shale gas wells.Recent research has demonstrated the existence of a multi-stage isotope fractionation phenomenon during shale gas production,with the fractionation characteristics of each stage associated with the pore structure,gas in place(GIP),adsorption/desorption,and gas production process.This study presents a new approach for estimating shale gas well production and evaluating the adsorbed/free gas ratio throughout production using isotope fractionation techniques.A reservoir-scale carbon isotope fractionation(CIF)model applicable to the production process of shale gas wells was developed for the first time in this research.In contrast to the traditional model,this model improves production prediction accuracy by simultaneously fitting the gas production rate and δ^(13)C_(1) data and provides a new evaluation method of the adsorbed/free gas ratio during shale gas production.The results indicate that the diffusion and adsorption/desorption properties of rock,bottom-hole flowing pressure(BHP)of gas well,and multi-scale gas transport regions of the reservoir all affect isotope fractionation,with the diffusion and adsorption/desorption parameters of rock having the greatest effect on isotope fractionation being D∗/D,PL,VL,α,and others in that order.We effectively tested the universality of the four-stage isotope fractionation feature and revealed a unique isotope fractionation mechanism caused by the superimposed coupling of multi-scale gas transport regions during shale gas well production.Finally,we applied the established CIF model to a shale gas well in the Sichuan Basin,China,and calculated the estimated ultimate recovery(EUR)of the well to be 3.33×10^(8) m^(3);the adsorbed gas ratio during shale gas production was 1.65%,10.03%,and 23.44%in the first,fifth,and tenth years,respectively.The findings are significant for understanding the isotope fractionation mechanism during natural gas transport in complex systems and for formulating and optimizing unconventional natural gas development strategies.展开更多
Water-soluble organic matter(WSOM)significantly influences the transport of metals and organic contaminants in soils,yet the interaction specifics with antimony(Sb)remain largely unexplored.Antimony is of particular e...Water-soluble organic matter(WSOM)significantly influences the transport of metals and organic contaminants in soils,yet the interaction specifics with antimony(Sb)remain largely unexplored.Antimony is of particular environmental concern due to its toxic properties and harmful effects on ecosystems and human health.Employing a three-step fractionation method with polyvinylpyrrolidone(PVP),this study aimed to isolate and analyze humic acids(HA),PVP-non adsorbed fulvic acids(FAA),and PVP-adsorbed fulvic acids(FAB)from WSOM in soil spiked with Sb and incubated for 18 months.These fractions underwent chemical analysis for carbon(C),nitrogen(N),total organic carbon(TOC),and Sb,complemented by FTIR and 1H NMR spectroscopic characterization.The study revealed that HA wasmore aliphatic,with Sb predominantly associating with the fulvic acid(FA)fraction,accounting for 97%of Sb in extracts.Specifically,the FAA subfraction held substantial portions of total carbon(TC),total nitrogen(TN),total organic carbon(TOC),and Sb.Correlations between Sb concentrations and TN,TC,and TOC were significant.Extraction methods showed NaOH and Na_(4)P_(2)O_(7) outperformed HCl and deionised water in extracting TC,TN,and TOC,with higher Sb concentrations found in Na_(4)P_(2)O_(7) and NaOH extracts.This underscores the role of Fe/Al-SOM complexes in Sb soil availability.The results revealed that FAA subfraction accounted for 76%,64%and 94%of TN,TOC and Sb,respectively.Therefore,this research highlights the FAA fraction’s central role,predominantly comprising non-humic substances like amines,in the availability of C,N,and Sb in Sb-impacted soils.The findings offer insights for environmental management and remediation strategies.展开更多
Based on geochemical data from natural gas samples across spring water systems and sedimentary basins,including Songliao,Bohai Bay,Sanshui,Sichuan,Ordos,Tarim and Ying-Qiong,this paper systematically compares the geoc...Based on geochemical data from natural gas samples across spring water systems and sedimentary basins,including Songliao,Bohai Bay,Sanshui,Sichuan,Ordos,Tarim and Ying-Qiong,this paper systematically compares the geochemical compositions of abiogenic versus biogenic gases.Emphasis is placed on the diagnostic signatures of abiogenic gases in terms of gas composition,and carbon,hydrogen and helium isotopes.The main findings are as follows.(1)In hydrothermal spring systems,abiogenic alkane gases are extremely scarce.Methane concentrations are typically less than 1%,with almost no detectable C^(2+)hydrocarbons.The gas is dominantly composed of CO_(2),while N_(2)is the major component in a few samples.(2)Abiogenic alkane gases display distinct isotopic signatures,including enriched methane carbon isotopic compositions(δ^(13)C_(1)>-25‰generally),complete carbon isotopic reversal(δ^(13)C_(1)>δ^(13)C_(2)>δ^(13)C_(3)>δ^(13)C_(4)),and enriched helium isotope(R/Ra>0.5,CH_(4)/^(3)He≤10^(6)generally).(3)The hydrogen isotopic composition of abiogenic alkane gases may be characterized by a positive sequence(δD_(1)<δD_(2)<δD_(3)),or a complete reversal(δD_(1)>δD_(2)>δD_(3)),or a V-shaped distribution(δD_(1)>δD_(2),δD_(2)<δD_(3)).The hydrogen isotopic compositions of methane generally show limited variation(about 9‰),possibly due to hydrogen isotopic exchange with connate water.(4)In terms of identifying gas origin,CH_(4)/^(3)He-R/Ra andδ^(13)CCO_(2)-R/Ra charts are more effective than CO_(2)/^(3)He-R/Ra chart.These new geological insights provide theoretical clues and diagnostic charts for the genetic identification of natural gas and further research on abiogenic gases.展开更多
Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferou...Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferous Benxi Formation were selected to conduct physical simulation and isotope monitoring experiments of the full-life-cycle depletion development of coal-rock gas.Based on the experimental results,a dual-medium carbon isotope fractionation(CIF)model coupling cleats/fractures and matrix pores was constructed,and an evaluation method for free gas production patterns was established to elucidate the carbon isotope fractionation mechanism and adsorbed/free gas production characteristics during deep coal-rock gas development.The results show that the deep coal-rock gas development process exhibits a three-stage carbon isotope fractionation pattern:“Stable(Ⅰ)→Decrease(Ⅱ)→Increase(Ⅲ)”.A rapid decline in boundary pressure in stageⅢleads to fluctuations in isotope value,characterized by a“rapid decrease followed by continued increase”,with free gas being produced first and long-term supply of adsorbed gas.The CIF model can effectively match measured gas pressure,cumulative gas production,and δ^(13)C_(1) value of produced gas.During the first two stages of isotope fractionation,free gas dominated cumulative production.During the mid-late stages of slow depletion production,the staged pressure control development method can effectively increase the gas recovery.The production of adsorbed gas is primarily controlled by the rock's adsorption capacity and the presence of secondary flow channels.Effectively enhancing the recovery of adsorbed gas during the late stage remains crucial for maintaining stable production and improving the ultimate recovery factor of deep coal-rock gas.展开更多
Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not y...Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.展开更多
Stable Sr isotopic composition(δ^(88/86)Sr)can be used to study magmatic processes,but their fractionation mechanism during magmatic evolution remains unclear.To understand the fractionation behaviors of the stable S...Stable Sr isotopic composition(δ^(88/86)Sr)can be used to study magmatic processes,but their fractionation mechanism during magmatic evolution remains unclear.To understand the fractionation behaviors of the stable Sr isotopes during magmatism,we report theδ^(88/86)Sr values of the Huili granitic pluton,which was subjected to intensive crystal-melt separation.The Huili pluton consists of K-feldspar granite and more evolved albite granite,and the albite granite exhibits significantly higherδ^(88/86)Sr values(+0.36‰to+0.52‰)than that of K-feldspar granite(+0.11‰to+0.25‰).K-feldspar,which contributes most of the Sr budget of the K-feldspar granite,has slightly lowerδ^(88/86)Sr values(−0.01‰to+0.17‰)than the whole rock.Theδ^(88/86)Sr variation of the Huili granites can be explained by separation of melt from K-feldspar-dominated crystals,because crystallization of K-feldspar can result in heavy Sr isotopic composition of the extracted interstitial melt.Stable Sr and Ba isotopic ratios in the Huili granites are highly coupled toward the heavy direction,refl ecting their similar element partitioning and isotope fractionation behaviors between the crystalline K-feldspar and melt.This study indicates that melt extraction plays a key role in granitic magma evolution.展开更多
The lack of understanding of heavy metal speciation and solubility control mechanisms in smelting soils limits the effective pollution control.In this study smelting soils were investigated by an advanced mineralogica...The lack of understanding of heavy metal speciation and solubility control mechanisms in smelting soils limits the effective pollution control.In this study smelting soils were investigated by an advanced mineralogical analysis(AMICS),leaching tests and thermodynamic modelling.The aims were to identify the partitioning and release behaviour of Pb,Zn,Cd and As.The integration of multiple techniques was necessary and displayed coherent results.In addition to the residual fraction,Pb and Zn were predominantly associated with reducible fractions,and As primarily existed as the crystalline iron oxide-bound fractions.AMICS quantitative analysis further confirmed that Fe oxyhydroxides were the common dominant phase for As,Cd,Pb and Zn.In addition,a metal arsenate(paulmooreite)was an important mineral host for Pb and As.The pH-stat leaching indicted that the release of Pb,Zn and Cd increased towards low pH values while release of As increased towards high p H values.The separate leaching schemes were associated with the geochemical behaviour under the control of minerals and were confirmed by thermodynamic modelling.PHREEQC calculations suggested that the formation of arsenate minerals(schultenite,mimetite and koritnigite)and the binding to Fe oxyhydroxides synchronously controlled the release of Pb,Zn,Cd and As.Our results emphasized the governing role of Fe oxyhydroxides and secondary insoluble minerals in natural attenuation of heavy metals,which provides a novelty strategy for the stabilization of multi-metals in smelting sites.展开更多
The phenomenon of carbon isotopic fractionation,induced by the transport of methane in tight sedimentary rocks through processes primarily involving diffusion and adsorption/desorption,is ubiquitous in nature and play...The phenomenon of carbon isotopic fractionation,induced by the transport of methane in tight sedimentary rocks through processes primarily involving diffusion and adsorption/desorption,is ubiquitous in nature and plays a significant role in numerous geological and geochemical systems.Consequently,understanding the mechanisms of transport-induced carbon isotopic fractionation both theoretically and experimentally is of considerable scientific importance.However,previous experimental studies have observed carbon isotope fractionation phenomena that are entirely distinct,and even exhibit opposing characteristics.At present,there is a lack of a convincing mechanistic explanation and valid numerical model for this discrepancy.Here,we performed gas transport experiments under different gas pressures(1–5 MPa)and confining pressures(10–20 MPa).The results show that methane carbon isotope fractionation during natural gas transport through shale is controlled by its pore structure and evolves regularly with increasing effective stress.Compared with the carbon isotopic composition of the source gas,the initial effluent methane is predominantly depleted in^(13)C,but occasionally exhibits^(13)C enrichment.The carbon isotopic composition of effluent methane converges to that of the source gas as mass transport reaches a steady state.The evolution patterns of the isotope fractionation curve,transitioning from the initial non-steady state to the final steady state,can be categorized into five distinct types.The combined effect of multi-level transport channels offers the most compelling mechanistic explanation for the observed evolution patterns and their interconversion.Numerical simulation studies demonstrate that existing models,including the Rayleigh model,the diffusion model,and the coupled diffusion-adsorption/desorption model,are unable to describe the observed complex isotope fractionation behavior.In contrast,the multi-scale multi-mechanism coupled model developed herein,incorporating diffusion and adsorption/desorption across multi-level transport channels,effectively reproduces all the observed fractionation patterns and supports the mechanistic rationale for the combined effect.Finally,the potential carbon isotopic fractionation resulting from natural gas transport in/through porous media and its geological implications are discussed in several hypothetical scenarios combining numerical simulations.These findings highlight the limitations of carbon isotopic parameters for determining the origin and maturity of natural gas,and underscore their potential in identifying greenhouse gas leaks and tracing sources.展开更多
Lack of information regarding lithium(Li)crystal chemistry in numerous minerals,especially those containing trace amounts of Li(ranging from a few to tens of ppm),limits our understanding of Li isotopic fractionation ...Lack of information regarding lithium(Li)crystal chemistry in numerous minerals,especially those containing trace amounts of Li(ranging from a few to tens of ppm),limits our understanding of Li isotopic fractionation in pegmatites.In this study,we examined the Li isotopic composition and Li content in various Li-poor(e.g.,quartz or feldspar)together with Li-rich(sopdumene or lepidolite)mineral phases within granitic pegmatites.We compiled a comprehensive dataset,encompassing a broad spectrum of Li contents(ranging from a few to tens of thousands of ppm)and Li isotopic values(-8‰to 41‰).The minerals exhibit distinct Li isotopic signatures.Specifically,elbaite and beryl show the highest values,while biotite displays a negative average.Compared to individual minerals,whole rocks demonstrate lower Li isotopic values,with pegmatites exhibiting the highest and non-granitic pegmatite wall rocks showing the lowest.Our study also uncovers a clear“V”shape relationship between Li isotopic values and logarithm of Li contents,with different mineral groups occupying specific regions within this shape.Furthermore,a significant correlation was observed between average Li isotopic values and Li-O(OH,F)bond lengths in various minerals.These discoveries underscore the crucial role of crystal chemistry in shaping the Li isotopic behavior in pegmatites from a statistical perspective.展开更多
Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations o...Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations of laboratory experiments due to its oversimplified assumptions.Here,we point out that the Hertz-Knudsen-equation-based theory is incomplete for silicate melt evaporation cases and can only be used for situations where the vaporized species is identical to the one in the melt.We propose a new model designed for silicate melt evaporation under vacuum.Our model considers multiple steps including mass transfer,chemical reaction,and nucleation.Our derivations reveal a kinetic isotopic fractionation factor(KIFF orα)αour model=[m(^(1)species)/m(^(2)species)]^(0.5),where m(species)is the mass of the reactant of reaction/nucleation-limiting step or species of diffusion-limiting step and superscript 1 and 2 represent light and heavy isotopes,respectively.This model can eff ectively reproduce most reported KIFFs of laboratory experiments for various elements,i.e.,Mg,Si,K,Rb,Fe,Ca,and Ti.And,the KIFF-mixing model referring that an overall rate of evaporation can be determined by two steps jointly can account for the eff ects of low P_(H2)pressure,composition,and temperature.In addition,we find that chemical reactions,diffusion,and nucleation can control the overall rate of evaporation of silicate melts by using the fitting slope in ln(−ln f)versus ln(t).Notably,our model allows for the theoretical calculations of parameters like activation energy(E_(a)),providing a novel approach to studying compositional and environmental eff ects on evaporation processes,and shedding light on the formation and evolution of the proto-solar and Earth-Moon systems.展开更多
It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the ef...It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the effect of the NVE on these kinetic processes is not known.The total fractionations(MDFs+NVEinduced MIFs)of several representative Hg-incorporated substances were selected and calculated with ab initio calculations in this work for both equilibrium and kinetic processes.NVE-induced MIFs were calculated with scaled contact electron densities at the nucleus through systematic evaluations of their accuracy and errors using the Gaussian09 and DIRAC19 packages(named the electron density scaling method).Additionally,the NVE-induced kinetic isotope effect(KIE)of Hg isotopes are also calculated with this method for several representative Hg oxidation reactions by chlorine species.Total KIEs for 202 Hg/^(198)Hg ranging from−2.27‰to 0.96‰are obtained.Three anomalous^(202)Hg-enriched KIEs(δ^(202)Hg/^(198)Hg=0.83‰,0.94‰,and 0.96‰,)caused by the NVE are observed,which are quite different from the classical view(i.e.,light isotopes react faster than the heavy ones).The electron density scaling method we developed in this study can provide an easier way to calculate the NVE-induced KIEs for heavy isotopes and serve to better understand the fractionation mechanisms of mercury isotope systems.展开更多
The aim of this study was to investigate the inter-fraction variations, patient comfort and knowledge at Charlotte Maxeke Johannesburg Academic Hospital (CMJAH). The differences in set-up that occurred between treatme...The aim of this study was to investigate the inter-fraction variations, patient comfort and knowledge at Charlotte Maxeke Johannesburg Academic Hospital (CMJAH). The differences in set-up that occurred between treatment sessions for the left sided breast patients were observed and recorded. Measurements of routine set-up variation for 24 patients were performed by matching the cone beam computed tomography (CBCT) and the planning computed tomography (CT). Scans of all five fractions per patient were used to quantify the setup variations with standard deviation (SD) in all the three directions (anterior posterior, left right, and superior inferior). The patients DIBH comfort and knowledge was also evaluated. The average translational errors for the anterior posterior (AP, z), left-right (LR, x), and Superior-inferior (SI, y) directions were 0.40 cm, 0.40 cm, and 0.40 cm, respectively. The translation variation of the three directions showed statistical significance (P < 0.05). On comfort and knowledge investigation, among all participants, 80% moderately agreed that the therapist’s instructions for operating the deep inspiration breath hold (DIBH) technique were easy to understand, and 63.33% indicated that their comfort with the DIBH technique was neutral or average. The inter-fraction variations in patients with left-sided breast cancer were qualitatively analyzed. Significant shifts between CBCT and planning CT images were observed. The daily treatment verification could assist accurate dose delivery.展开更多
【目的】分析新疆小麦品种资源蛋白质品质性状和贮藏蛋白组分的遗传多样性及其关系,为拓宽新疆小麦品种资源的遗传基础及育种的亲本选配和品种选育提供优质亲本材料。【方法】以303份新疆小麦品种资源为材料,对其蛋白质品质性状和贮藏...【目的】分析新疆小麦品种资源蛋白质品质性状和贮藏蛋白组分的遗传多样性及其关系,为拓宽新疆小麦品种资源的遗传基础及育种的亲本选配和品种选育提供优质亲本材料。【方法】以303份新疆小麦品种资源为材料,对其蛋白质品质性状和贮藏蛋白组分含量进行变异、相关及聚类分析,并计算其遗传多样性指数(H')和隶属函数值,对供试材料进行综合评价。【结果】新疆小麦品种资源蛋白质品质性状和贮藏蛋白组分含量的变异系数范围分别为5.52%—60.99%和9.17%—23.69%,变异系数最大的为8分钟宽度;贮藏蛋白组分含量的变异系数最大为不溶性谷蛋白聚合体含量(UPP);遗传多样性指数分别为1.06—2.15,平均为1.78,其中,面筋指数最大,为2.15,峰值时间最小,为1.06。相关分析、多元回归分析表明,综合评价值(F_(15))可以评价蛋白品质(面筋质量)的优劣;面筋指数(GI)、峰值时间(PT)、8分钟宽度(8 min width)、沉淀值(SV)和不溶性谷蛋白聚合体含量(UPP)指标是评价蛋白品质的重要性状,可在今后的育种中加以应用。经聚类分析,将303份小麦品种资源分为三类,所占比例分别为15.84%、43.23%和40.92%,3个类群中,第Ⅰ类群的综合评价值表现最高,品质指标表现最优,其中,不溶性谷蛋白聚合体百分含量(%UPP)、不溶性谷蛋白聚合体含量(UPP)、面筋指数(GI)、峰值时间(PT)、8分钟宽度(8 min width)、8分钟面积(8 min area)、沉淀值(SV)等7个指标的平均值均显著最高,表明通过F_(15)评价面筋质量的优劣是可靠的。【结论】明确了新疆冬小麦品种资源蛋白质品质性状和贮藏蛋白组分指标的遗传多样性分布特点及关系,筛选出评价蛋白质品质的重要性状,基于综合评价值(F_(15))筛选出一批贮藏蛋白组分与小麦蛋白质品质性状综合表现优异的资源,可在今后的育种中加以利用。展开更多
基金supported by the Fundamental Research Funds for the Central Universities(QNTD202302)National Natural Science Foundation of China(22378024)the Foreign expert program(G2022109001L).
文摘Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin first”strategy,corn straw is converted to valuable chemicals including lignin monomers,furfural and 5-methoxymethylfurfural via a two steps process.The key of this research lies in the development of a green and low-cost catalytic process utilizing magnetic Raney Ni catalyst and high boiling point ethylene glycol.The utilization of neat ethylene glycol as the sole slovent under atmospheric conditions obviates the need for additional additives,thereby facilitating the entire process to be conducted in glass flasks and rendering it highly convenient for scaling up.In the initial step,depolymerization of corn straw lignin resulted in a monomer yield of 18.1 wt%.Subsequently,in a dimethyl carbonate system,the carbohydrate component underwent complete conversion in a one-pot process,yielding furfural and 5-methoxymethylfurfural as the primary products with an impressive yield of 47.7%.
基金supported by the Natural Science Foundation of China(Grant No.42302170)National Postdoctoral Innovative Talent Support Program(Grant No.BX20220062)+3 种基金CNPC Innovation Found(Grant No.2022DQ02-0104)National Science Foundation of Heilongjiang Province of China(Grant No.YQ2023D001)Postdoctoral Science Foundation of Heilongjiang Province of China(Grant No.LBH-Z22091)the Natural Science Foundation of Shandong Province(Grant No.ZR2022YQ30).
文摘Prediction of production decline and evaluation of the adsorbed/free gas ratio are critical for determining the lifespan and production status of shale gas wells.Traditional production prediction methods have some shortcomings because of the low permeability and tightness of shale,complex gas flow behavior of multi-scale gas transport regions and multiple gas transport mechanism superpositions,and complex and variable production regimes of shale gas wells.Recent research has demonstrated the existence of a multi-stage isotope fractionation phenomenon during shale gas production,with the fractionation characteristics of each stage associated with the pore structure,gas in place(GIP),adsorption/desorption,and gas production process.This study presents a new approach for estimating shale gas well production and evaluating the adsorbed/free gas ratio throughout production using isotope fractionation techniques.A reservoir-scale carbon isotope fractionation(CIF)model applicable to the production process of shale gas wells was developed for the first time in this research.In contrast to the traditional model,this model improves production prediction accuracy by simultaneously fitting the gas production rate and δ^(13)C_(1) data and provides a new evaluation method of the adsorbed/free gas ratio during shale gas production.The results indicate that the diffusion and adsorption/desorption properties of rock,bottom-hole flowing pressure(BHP)of gas well,and multi-scale gas transport regions of the reservoir all affect isotope fractionation,with the diffusion and adsorption/desorption parameters of rock having the greatest effect on isotope fractionation being D∗/D,PL,VL,α,and others in that order.We effectively tested the universality of the four-stage isotope fractionation feature and revealed a unique isotope fractionation mechanism caused by the superimposed coupling of multi-scale gas transport regions during shale gas well production.Finally,we applied the established CIF model to a shale gas well in the Sichuan Basin,China,and calculated the estimated ultimate recovery(EUR)of the well to be 3.33×10^(8) m^(3);the adsorbed gas ratio during shale gas production was 1.65%,10.03%,and 23.44%in the first,fifth,and tenth years,respectively.The findings are significant for understanding the isotope fractionation mechanism during natural gas transport in complex systems and for formulating and optimizing unconventional natural gas development strategies.
基金financial support provided by the University of New England,Australia for conducting this research。
文摘Water-soluble organic matter(WSOM)significantly influences the transport of metals and organic contaminants in soils,yet the interaction specifics with antimony(Sb)remain largely unexplored.Antimony is of particular environmental concern due to its toxic properties and harmful effects on ecosystems and human health.Employing a three-step fractionation method with polyvinylpyrrolidone(PVP),this study aimed to isolate and analyze humic acids(HA),PVP-non adsorbed fulvic acids(FAA),and PVP-adsorbed fulvic acids(FAB)from WSOM in soil spiked with Sb and incubated for 18 months.These fractions underwent chemical analysis for carbon(C),nitrogen(N),total organic carbon(TOC),and Sb,complemented by FTIR and 1H NMR spectroscopic characterization.The study revealed that HA wasmore aliphatic,with Sb predominantly associating with the fulvic acid(FA)fraction,accounting for 97%of Sb in extracts.Specifically,the FAA subfraction held substantial portions of total carbon(TC),total nitrogen(TN),total organic carbon(TOC),and Sb.Correlations between Sb concentrations and TN,TC,and TOC were significant.Extraction methods showed NaOH and Na_(4)P_(2)O_(7) outperformed HCl and deionised water in extracting TC,TN,and TOC,with higher Sb concentrations found in Na_(4)P_(2)O_(7) and NaOH extracts.This underscores the role of Fe/Al-SOM complexes in Sb soil availability.The results revealed that FAA subfraction accounted for 76%,64%and 94%of TN,TOC and Sb,respectively.Therefore,this research highlights the FAA fraction’s central role,predominantly comprising non-humic substances like amines,in the availability of C,N,and Sb in Sb-impacted soils.The findings offer insights for environmental management and remediation strategies.
基金Supported by PetroChina Science and Technology Research and Technology Development Project(2021DJ0502)Open Research Project of Key Laboratory of Shale Gas Resources Exploration,Ministry of Natural Resources(Chongqing Institute of Geology and Mineral Resources)(KLSGE-2023).
文摘Based on geochemical data from natural gas samples across spring water systems and sedimentary basins,including Songliao,Bohai Bay,Sanshui,Sichuan,Ordos,Tarim and Ying-Qiong,this paper systematically compares the geochemical compositions of abiogenic versus biogenic gases.Emphasis is placed on the diagnostic signatures of abiogenic gases in terms of gas composition,and carbon,hydrogen and helium isotopes.The main findings are as follows.(1)In hydrothermal spring systems,abiogenic alkane gases are extremely scarce.Methane concentrations are typically less than 1%,with almost no detectable C^(2+)hydrocarbons.The gas is dominantly composed of CO_(2),while N_(2)is the major component in a few samples.(2)Abiogenic alkane gases display distinct isotopic signatures,including enriched methane carbon isotopic compositions(δ^(13)C_(1)>-25‰generally),complete carbon isotopic reversal(δ^(13)C_(1)>δ^(13)C_(2)>δ^(13)C_(3)>δ^(13)C_(4)),and enriched helium isotope(R/Ra>0.5,CH_(4)/^(3)He≤10^(6)generally).(3)The hydrogen isotopic composition of abiogenic alkane gases may be characterized by a positive sequence(δD_(1)<δD_(2)<δD_(3)),or a complete reversal(δD_(1)>δD_(2)>δD_(3)),or a V-shaped distribution(δD_(1)>δD_(2),δD_(2)<δD_(3)).The hydrogen isotopic compositions of methane generally show limited variation(about 9‰),possibly due to hydrogen isotopic exchange with connate water.(4)In terms of identifying gas origin,CH_(4)/^(3)He-R/Ra andδ^(13)CCO_(2)-R/Ra charts are more effective than CO_(2)/^(3)He-R/Ra chart.These new geological insights provide theoretical clues and diagnostic charts for the genetic identification of natural gas and further research on abiogenic gases.
基金Youth Fund of National Natural Science Foundation of China(42302170)CNPC Scientific and Technological Innovation Fund(2022DQ02-0104)RIPED Open Project Fund(2024-KFKT-31).
文摘Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferous Benxi Formation were selected to conduct physical simulation and isotope monitoring experiments of the full-life-cycle depletion development of coal-rock gas.Based on the experimental results,a dual-medium carbon isotope fractionation(CIF)model coupling cleats/fractures and matrix pores was constructed,and an evaluation method for free gas production patterns was established to elucidate the carbon isotope fractionation mechanism and adsorbed/free gas production characteristics during deep coal-rock gas development.The results show that the deep coal-rock gas development process exhibits a three-stage carbon isotope fractionation pattern:“Stable(Ⅰ)→Decrease(Ⅱ)→Increase(Ⅲ)”.A rapid decline in boundary pressure in stageⅢleads to fluctuations in isotope value,characterized by a“rapid decrease followed by continued increase”,with free gas being produced first and long-term supply of adsorbed gas.The CIF model can effectively match measured gas pressure,cumulative gas production,and δ^(13)C_(1) value of produced gas.During the first two stages of isotope fractionation,free gas dominated cumulative production.During the mid-late stages of slow depletion production,the staged pressure control development method can effectively increase the gas recovery.The production of adsorbed gas is primarily controlled by the rock's adsorption capacity and the presence of secondary flow channels.Effectively enhancing the recovery of adsorbed gas during the late stage remains crucial for maintaining stable production and improving the ultimate recovery factor of deep coal-rock gas.
基金supported by the National Natural Science Foundation of China(U21A2033)the Fundamental Research Funds for the Central Universities(2652022103).
文摘Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.
基金supported by National Natural Science Foundation of China(42473009).
文摘Stable Sr isotopic composition(δ^(88/86)Sr)can be used to study magmatic processes,but their fractionation mechanism during magmatic evolution remains unclear.To understand the fractionation behaviors of the stable Sr isotopes during magmatism,we report theδ^(88/86)Sr values of the Huili granitic pluton,which was subjected to intensive crystal-melt separation.The Huili pluton consists of K-feldspar granite and more evolved albite granite,and the albite granite exhibits significantly higherδ^(88/86)Sr values(+0.36‰to+0.52‰)than that of K-feldspar granite(+0.11‰to+0.25‰).K-feldspar,which contributes most of the Sr budget of the K-feldspar granite,has slightly lowerδ^(88/86)Sr values(−0.01‰to+0.17‰)than the whole rock.Theδ^(88/86)Sr variation of the Huili granites can be explained by separation of melt from K-feldspar-dominated crystals,because crystallization of K-feldspar can result in heavy Sr isotopic composition of the extracted interstitial melt.Stable Sr and Ba isotopic ratios in the Huili granites are highly coupled toward the heavy direction,refl ecting their similar element partitioning and isotope fractionation behaviors between the crystalline K-feldspar and melt.This study indicates that melt extraction plays a key role in granitic magma evolution.
基金funded by the National Key Research and Development Program of China(No.2019YFC1803601)the National Natural Science Foundation of China(No.42177392)the Fundamental Research Funds for the Central Universities of Central South University(No.2021zzts0122)。
文摘The lack of understanding of heavy metal speciation and solubility control mechanisms in smelting soils limits the effective pollution control.In this study smelting soils were investigated by an advanced mineralogical analysis(AMICS),leaching tests and thermodynamic modelling.The aims were to identify the partitioning and release behaviour of Pb,Zn,Cd and As.The integration of multiple techniques was necessary and displayed coherent results.In addition to the residual fraction,Pb and Zn were predominantly associated with reducible fractions,and As primarily existed as the crystalline iron oxide-bound fractions.AMICS quantitative analysis further confirmed that Fe oxyhydroxides were the common dominant phase for As,Cd,Pb and Zn.In addition,a metal arsenate(paulmooreite)was an important mineral host for Pb and As.The pH-stat leaching indicted that the release of Pb,Zn and Cd increased towards low pH values while release of As increased towards high p H values.The separate leaching schemes were associated with the geochemical behaviour under the control of minerals and were confirmed by thermodynamic modelling.PHREEQC calculations suggested that the formation of arsenate minerals(schultenite,mimetite and koritnigite)and the binding to Fe oxyhydroxides synchronously controlled the release of Pb,Zn,Cd and As.Our results emphasized the governing role of Fe oxyhydroxides and secondary insoluble minerals in natural attenuation of heavy metals,which provides a novelty strategy for the stabilization of multi-metals in smelting sites.
基金the National Natural Science Foundation of China(Grant Nos.42302170,42302160)the Innovation Platform for Academicians of Hainan Province(YSPTZX202301)+3 种基金the National Postdoctoral Innovative Talent Support Program(Grant No.BX20220062)the National Science Foundation of Heilongjiang Province of China(Grant No.YQ2023D001)the Project of Sanya Yazhou Bay Science and Technology City(Grant No.SCKJ-JYRC-2023-01)CNPC Innovation Found(Grant No.2022DQ02-0104).
文摘The phenomenon of carbon isotopic fractionation,induced by the transport of methane in tight sedimentary rocks through processes primarily involving diffusion and adsorption/desorption,is ubiquitous in nature and plays a significant role in numerous geological and geochemical systems.Consequently,understanding the mechanisms of transport-induced carbon isotopic fractionation both theoretically and experimentally is of considerable scientific importance.However,previous experimental studies have observed carbon isotope fractionation phenomena that are entirely distinct,and even exhibit opposing characteristics.At present,there is a lack of a convincing mechanistic explanation and valid numerical model for this discrepancy.Here,we performed gas transport experiments under different gas pressures(1–5 MPa)and confining pressures(10–20 MPa).The results show that methane carbon isotope fractionation during natural gas transport through shale is controlled by its pore structure and evolves regularly with increasing effective stress.Compared with the carbon isotopic composition of the source gas,the initial effluent methane is predominantly depleted in^(13)C,but occasionally exhibits^(13)C enrichment.The carbon isotopic composition of effluent methane converges to that of the source gas as mass transport reaches a steady state.The evolution patterns of the isotope fractionation curve,transitioning from the initial non-steady state to the final steady state,can be categorized into five distinct types.The combined effect of multi-level transport channels offers the most compelling mechanistic explanation for the observed evolution patterns and their interconversion.Numerical simulation studies demonstrate that existing models,including the Rayleigh model,the diffusion model,and the coupled diffusion-adsorption/desorption model,are unable to describe the observed complex isotope fractionation behavior.In contrast,the multi-scale multi-mechanism coupled model developed herein,incorporating diffusion and adsorption/desorption across multi-level transport channels,effectively reproduces all the observed fractionation patterns and supports the mechanistic rationale for the combined effect.Finally,the potential carbon isotopic fractionation resulting from natural gas transport in/through porous media and its geological implications are discussed in several hypothetical scenarios combining numerical simulations.These findings highlight the limitations of carbon isotopic parameters for determining the origin and maturity of natural gas,and underscore their potential in identifying greenhouse gas leaks and tracing sources.
基金financially supported by the Second Tibetan Plateau Scientific Expedition and Research Program(STEP)(No.2019QZKK0802)。
文摘Lack of information regarding lithium(Li)crystal chemistry in numerous minerals,especially those containing trace amounts of Li(ranging from a few to tens of ppm),limits our understanding of Li isotopic fractionation in pegmatites.In this study,we examined the Li isotopic composition and Li content in various Li-poor(e.g.,quartz or feldspar)together with Li-rich(sopdumene or lepidolite)mineral phases within granitic pegmatites.We compiled a comprehensive dataset,encompassing a broad spectrum of Li contents(ranging from a few to tens of thousands of ppm)and Li isotopic values(-8‰to 41‰).The minerals exhibit distinct Li isotopic signatures.Specifically,elbaite and beryl show the highest values,while biotite displays a negative average.Compared to individual minerals,whole rocks demonstrate lower Li isotopic values,with pegmatites exhibiting the highest and non-granitic pegmatite wall rocks showing the lowest.Our study also uncovers a clear“V”shape relationship between Li isotopic values and logarithm of Li contents,with different mineral groups occupying specific regions within this shape.Furthermore,a significant correlation was observed between average Li isotopic values and Li-O(OH,F)bond lengths in various minerals.These discoveries underscore the crucial role of crystal chemistry in shaping the Li isotopic behavior in pegmatites from a statistical perspective.
基金supported by Chinese NSF project(42,130,114)the strategic priority research program(B)of CAS(XDB41000000)the pre-research Project on Civil Aerospace Technologies No.D020202 funded by Chinese National Space Administration(CNSA)and Guizhou Provincial 2021 Science and Technology Subsidies(No.GZ2021SIG).
文摘Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations of laboratory experiments due to its oversimplified assumptions.Here,we point out that the Hertz-Knudsen-equation-based theory is incomplete for silicate melt evaporation cases and can only be used for situations where the vaporized species is identical to the one in the melt.We propose a new model designed for silicate melt evaporation under vacuum.Our model considers multiple steps including mass transfer,chemical reaction,and nucleation.Our derivations reveal a kinetic isotopic fractionation factor(KIFF orα)αour model=[m(^(1)species)/m(^(2)species)]^(0.5),where m(species)is the mass of the reactant of reaction/nucleation-limiting step or species of diffusion-limiting step and superscript 1 and 2 represent light and heavy isotopes,respectively.This model can eff ectively reproduce most reported KIFFs of laboratory experiments for various elements,i.e.,Mg,Si,K,Rb,Fe,Ca,and Ti.And,the KIFF-mixing model referring that an overall rate of evaporation can be determined by two steps jointly can account for the eff ects of low P_(H2)pressure,composition,and temperature.In addition,we find that chemical reactions,diffusion,and nucleation can control the overall rate of evaporation of silicate melts by using the fitting slope in ln(−ln f)versus ln(t).Notably,our model allows for the theoretical calculations of parameters like activation energy(E_(a)),providing a novel approach to studying compositional and environmental eff ects on evaporation processes,and shedding light on the formation and evolution of the proto-solar and Earth-Moon systems.
基金This paper is supported by Chinese NSF project(42130114)the strategic priority research program(B)of CAS(XDB41000000)the pre-research Project on Civil Aerospace Technologies No.D020202 funded by Chinese National Space Administration(CNSA)。
文摘It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the effect of the NVE on these kinetic processes is not known.The total fractionations(MDFs+NVEinduced MIFs)of several representative Hg-incorporated substances were selected and calculated with ab initio calculations in this work for both equilibrium and kinetic processes.NVE-induced MIFs were calculated with scaled contact electron densities at the nucleus through systematic evaluations of their accuracy and errors using the Gaussian09 and DIRAC19 packages(named the electron density scaling method).Additionally,the NVE-induced kinetic isotope effect(KIE)of Hg isotopes are also calculated with this method for several representative Hg oxidation reactions by chlorine species.Total KIEs for 202 Hg/^(198)Hg ranging from−2.27‰to 0.96‰are obtained.Three anomalous^(202)Hg-enriched KIEs(δ^(202)Hg/^(198)Hg=0.83‰,0.94‰,and 0.96‰,)caused by the NVE are observed,which are quite different from the classical view(i.e.,light isotopes react faster than the heavy ones).The electron density scaling method we developed in this study can provide an easier way to calculate the NVE-induced KIEs for heavy isotopes and serve to better understand the fractionation mechanisms of mercury isotope systems.
文摘The aim of this study was to investigate the inter-fraction variations, patient comfort and knowledge at Charlotte Maxeke Johannesburg Academic Hospital (CMJAH). The differences in set-up that occurred between treatment sessions for the left sided breast patients were observed and recorded. Measurements of routine set-up variation for 24 patients were performed by matching the cone beam computed tomography (CBCT) and the planning computed tomography (CT). Scans of all five fractions per patient were used to quantify the setup variations with standard deviation (SD) in all the three directions (anterior posterior, left right, and superior inferior). The patients DIBH comfort and knowledge was also evaluated. The average translational errors for the anterior posterior (AP, z), left-right (LR, x), and Superior-inferior (SI, y) directions were 0.40 cm, 0.40 cm, and 0.40 cm, respectively. The translation variation of the three directions showed statistical significance (P < 0.05). On comfort and knowledge investigation, among all participants, 80% moderately agreed that the therapist’s instructions for operating the deep inspiration breath hold (DIBH) technique were easy to understand, and 63.33% indicated that their comfort with the DIBH technique was neutral or average. The inter-fraction variations in patients with left-sided breast cancer were qualitatively analyzed. Significant shifts between CBCT and planning CT images were observed. The daily treatment verification could assist accurate dose delivery.
文摘【目的】分析新疆小麦品种资源蛋白质品质性状和贮藏蛋白组分的遗传多样性及其关系,为拓宽新疆小麦品种资源的遗传基础及育种的亲本选配和品种选育提供优质亲本材料。【方法】以303份新疆小麦品种资源为材料,对其蛋白质品质性状和贮藏蛋白组分含量进行变异、相关及聚类分析,并计算其遗传多样性指数(H')和隶属函数值,对供试材料进行综合评价。【结果】新疆小麦品种资源蛋白质品质性状和贮藏蛋白组分含量的变异系数范围分别为5.52%—60.99%和9.17%—23.69%,变异系数最大的为8分钟宽度;贮藏蛋白组分含量的变异系数最大为不溶性谷蛋白聚合体含量(UPP);遗传多样性指数分别为1.06—2.15,平均为1.78,其中,面筋指数最大,为2.15,峰值时间最小,为1.06。相关分析、多元回归分析表明,综合评价值(F_(15))可以评价蛋白品质(面筋质量)的优劣;面筋指数(GI)、峰值时间(PT)、8分钟宽度(8 min width)、沉淀值(SV)和不溶性谷蛋白聚合体含量(UPP)指标是评价蛋白品质的重要性状,可在今后的育种中加以应用。经聚类分析,将303份小麦品种资源分为三类,所占比例分别为15.84%、43.23%和40.92%,3个类群中,第Ⅰ类群的综合评价值表现最高,品质指标表现最优,其中,不溶性谷蛋白聚合体百分含量(%UPP)、不溶性谷蛋白聚合体含量(UPP)、面筋指数(GI)、峰值时间(PT)、8分钟宽度(8 min width)、8分钟面积(8 min area)、沉淀值(SV)等7个指标的平均值均显著最高,表明通过F_(15)评价面筋质量的优劣是可靠的。【结论】明确了新疆冬小麦品种资源蛋白质品质性状和贮藏蛋白组分指标的遗传多样性分布特点及关系,筛选出评价蛋白质品质的重要性状,基于综合评价值(F_(15))筛选出一批贮藏蛋白组分与小麦蛋白质品质性状综合表现优异的资源,可在今后的育种中加以利用。
