水溶性富勒烯对U(VI)在氧化多壁碳纳米管上吸附的影响

采用静态试验法研究了水溶性富勒烯对U(VI)在氧化多壁碳纳米管上吸附的影响。结果表明,羟基化富勒烯(C₆₀(OH)n)和羧基化富勒烯(C₆₀(C(COOH)₂)n)的加入对U(VI)在氧化多壁碳纳米管上的吸附量影响作用类似。在pH<3范围内,羟基化富勒烯和羧基化富勒烯对吸附几乎没有影响,在pH>3以后,二者开始抑制碳纳米管对U(VI)的吸附。较低浓度(10 mg/L)的C₆₀(OH)n对U(VI)的吸附几乎没有影响。而等量的C₆₀(C(COOH)₂)n已呈现出明显的抑制作用。但两者的作用机理不同,前者可能是由于羟基化富勒烯和U(VI)竞争氧化多壁碳纳米管上的吸附位点造成的,后者则可能改变了氧化多壁碳纳米管的表面电荷。用双位点模型对不同固液比和U(VI)初始浓度下U(VI)的吸附率随C₆₀(OH)n和C₆₀(C(COOH)₂)n初始浓度的变化进行了拟合得到了很好的结果。     

14C测定年代报告(一)

本文介绍了应用碳化理(Li₂C₂)法进行化学制样测定¹⁴C年代获得成功的试验.抑制鋰的升华作用是成功的关键.文中提出了改革鋰反应器冷却装置的根据和方案.试验结果是令人满意的.从CO₂到C₂H₂的转化中碳的收率高达98%(而S_tC₂法为70%左右).本文发表了40个¹⁴C年代数据,其中4个进行了互校对比,一致性很好.     

离子液体([C6MIm])从体相电迁移至水相研究

离子在离子液体/水溶液二元系统中的电迁移行为在很多领域受到了越来越多的关注。本文通过研究不同条件下离子液体离子在电极液中的浓度变化,系统地研究了电极溶液酸—碱度,电极溶液中电解质浓度以及离子液体中溶解LiN(CF₃SO₂)₂与否对[C₆MIm]⁺离子电迁移的影响。总的来说,随着电流的增加,[C₆MIm]⁺离子向阴极水溶液的迁移量随之增加,向阳极水溶液的迁移量随之减少;然而N(CF₃SO₂)₂-离子向阳极水溶液的迁移量随之增加,向阴极水溶液的迁移量随之减少。当电极溶液为碱性,[C₆MIm]⁺离子的迁移量明显减少。在电极溶液中溶入LiN(CF₃SO₂)₂时或者将LiN(CF₃SO₂)₂溶入离子液体时,[C₆MIm]⁺离子的迁移量也明显受到抑制。     

全球碳循环变化:生物界对大气圈中CO_2浓度变化反应的勒夏特利埃原理(报导Ⅱ)

大气中¹³C 变化的界限我们将认为,方程（24）和（25）中的所有经验数据,除Δδ¹³C_a 外,都是已知的,且精度较高。我们可把该式右部看做是Δδ¹³C_a的函数——在从17世纪开始的整个人为扰动时期内大气中¹³C_a 的相对含量变动量的变化。在方程（24）和（25）的实验数据中既有与时间无关的数值(σ,ζ,K_as,μ^*),又有随时间变化的数据(δ¹³C、Δx_a)。从1958年起就开始有系统地测量随时间变化的数据。     

Mg(BO2)2在MgSO4和MgCl2-MgSO4水溶液中分解的相平衡与物种化学平衡

硫酸镁亚型盐湖老卤是MgCl₂、MgSO₄的饱和溶液体系,富集了Mg、B、Li等元素。本文针对含硼水盐体系热力学难以表达的问题,开展了硼在水盐体系存在形态及其平衡关系的研究。利用易于水解的Mg(BO₂)₂作为硼源,借助拉曼光谱和X射线衍射(XRD)为检测手段,定量研究Mg(BO₂)₂在MgSO₄-H₂O、MgSO₄-MgCl₂-H₂O体系中水解硼物种转化规律。结果表明:(1)Mg(BO₂)₂在MgSO₄溶液中的水解固相为MgB₂O(OH)6、MgB₄O₇·9H₂O和Mg(OH)₂;在MgSO₄-MgCl₂-H₂O溶液中水解固相为Mg₂B₆O₁₁·15H₂O、MgB₄O₇·9H₂O、Mg₂Cl(OH)₃·4H₂O。(2)Mg(BO₂)₂在MgSO₄溶液中水解,液相硼物种主要有B₃O₃(OH)-₄、B₃O₃(OH)₅2-、B(OH)-₄、B₄O₅(OH)₄2-、H₃BO₃,其分布受MgSO₄浓度影响很大,MgSO₄浓度从0增加至饱和,B₃O₃(OH)-₄始终占总硼量的50.07%以上,B₃O₃(OH)₅2-占液相总硼从4.77%上升至37.16%为第2化学物种。(3)在MgSO₄-MgCl₂-H₂O溶液中,硼物种的主要形态有B₃O₃(OH)-₄、B₃O₃(OH)₅2-、B(OH)-₄,其分布 随[Cl₂2-]/([Cl₂2-]+[SO₄2-])变化很大,在MgCl₂和MgSO₄的共饱溶液中,分别占液相总硼量的58.91%,14.62%和12.81%。(4)液相硼物种之间平衡关系的活度商lnQ,不仅与溶液pH、水活度有关,还与MgSO₄、MgCl₂摩尔浓度呈二元线性关系,这样就可将硼在H₃BO₃-NaOH体系物种分布关系的lnQ扩展到 (MgSO₄,MgCl₂,MgSO₄-MgCl₂)水溶液的多元体系。由此获得硼物种的量化关系,可为推算硼在水盐体系的物种分布,进而计算含硼电解质溶液热力学性质提供依据。     

崇明东滩湿地CO2 、CH4和N2O 排放的时空差异

通过静态暗箱—气相色谱法研究了长江口崇明东滩四类典型湿地(围垦湿地、高潮滩、中潮滩和低潮滩)CO₂、CH₄和N₂O排放特征及影响因素。结果表明,在生长季尺度下,CO₂、CH₄和N₂O均以排放为主;在昼夜尺度下,CO₂和CH₄在夜间排放量大于白昼排放量,而N₂O的排放高峰出现在下午;在潮水退去、潮滩暴露初期,CH₄和N₂O有大量排放,CO₂正好相反。崇明东滩温室气体排放通量自岸向海有明显的梯度变化,总体趋势是越近岸通量值越大。观测与实验表明,温度、潮汐、土壤理化性质、植物和土地利用变化都对温室气体排放通量有明显的影响,其中滨海潮滩湿地特有环境因子潮汐以"淹没—暴露"光滩沉积物的方式控制温室气体的排放。     

KNO3溶液结构:密度泛函理论和分子动力学研究

基于密度泛函理论,采用ωB97XD方法和6-311++G(d,p)基组,系统研究了[K(H₂O)_n]⁺,[NO₃(H₂O)_n]-和KNO₃(H₂O)_n水合团簇的结构和性质;并结合经典分子动力学、OPLS-AA全原子力场以及SPC/E水模型模拟了不同水盐比(WSR) KNO₃溶液,目的在于深入理解KNO₃溶液中K⁺和 NO-₃的微观水合结构,以及K⁺-NO-₃离子间缔合作用特征。研究发现,对于KNO₃(H₂O)_n (n=6,8,10和12)水合团簇,K⁺第一水合层稳定结构为四、五和六水合结构,其中五水合结构最稳定。K⁺和NO-₃主要以溶剂共享离子对形式存在。随着团簇尺寸减小,直接接触离子对(CIP)物种出现。同时,分子动力学模拟证实KNO₃溶液中形成了直接接触K⁺-NO-₃离子对,且随着溶液浓度增加,CIP物种形成需越过更大能垒。以上结果表明在KNO₃稀溶液中主要存在物种为水合K⁺和NO-₃,随浓度增大,单齿直接接触离子对(MCIP)逐渐出现。在高浓溶液或过饱和溶液中,K⁺-NO-₃离子缔合主要以单齿CIP和少量双齿CIP结构存在。     

土壤盐分特征对内陆盐沼盐生植物群落的影响

为研究内陆盐沼植物群落的分布对土壤盐分的响应特征,选取鄂尔多斯盐湖盐沼区作为研究区,筛选了肉质耐盐植物群落,苔草植物群落和禾草植物群落3类典型植物群落,开展了土壤含水量、pH、电导率以及Na_⁺,K_⁺,Mg2_⁺,Ca_{^{2 +}},Cl_^-、SO_4^2-、CO_3^2-和HCO_3^-的测定,分析了区内典型植物群落对土壤水盐因子的响应规律。探讨了3类植物群落之间土壤因子含量的差异性;采用相关性分析和CCA分析,评价了3类植物群落多样性及物种分布随土壤因子的变化规律。结果表明,区内3类植物群落中,土壤盐分含量表现为肉质耐盐植物群落最高,苔草植物群落最低,禾草植物群落居中;植物多样性与土壤中含量最高的Na_⁺和SO_4^2-的相关性最显著;植物分布同时受到土壤盐分、水分和pH的显著影响。研究结果可为鄂尔多斯盐湖区土壤盐渍化改良和植被恢复提供理论支撑。     

Na+,K+,Rb+,Cs+//SO2-4-H2O体系固液相平衡热力学模拟

锂云母、铯榴石等矿物的硫酸盐焙烧浸出,是从中提取锂铷铯钾等碱金属元素的重要步骤,所得硫酸盐浸出液可近似看作Li⁺,Na⁺,K⁺,Rb⁺,Cs+ // SO₄2--H₂O六元水盐体系;其在浓缩过程呈现复杂的成盐特征,增加了各碱金属元素分离提取的难度,研究其相关水盐体系相图和相平衡性质对理解浸出液中碱金属的分离具有重要的理论指导意义。本文采用Pitzer-Simonson-Clegg超额Gibbs自由能方程和具有内在热力学一致性的CALPHAD方法,构建了Na⁺,K⁺,Rb⁺,Cs⁺//SO₄2--H₂O五元体系的多温固液相平衡热力学模型。借助该模型:1)实现了对Na₂SO₄₊Rb₂SO₄₊H₂O、Na₂SO₄₊Cs₂SO₄₊H₂O和K₂SO₄₊Cs₂SO₄₊H₂O三元体系的多温溶解度等温线的准确描述,并进一步构建了这些体系在240.15~380.15 K温度范围内的多温相图;2)实现了对K₂SO₄+Rb₂SO₄₊H₂O和Rb₂SO₄₊Cs₂SO₄₊H₂O体系中存在的固溶体相—水溶液平衡关系的准确描述,确认了(K,Rb)₂SO₄连续固溶体、以及(Rb,Cs)₂SO₄(α)和(Rb,Cs)₂SO₄(β)间断固溶体存在的合理性;3)预测了上述五元体系中所包含的全部4个四元子体系(Na₂SO₄₊ K₂SO₄₊ Rb₂SO₄+H₂O、Na₂SO₄ + K₂SO₄₊Cs₂SO₄₊ H₂O、Na₂SO₄₊ Rb₂SO₄₊Cs₂SO₄ + H₂O和K₂SO₄₊Rb₂SO₄₊Cs₂SO₄₊ H₂O)的相图,明确了四元相图中固溶体的类型及形成区域。然而,模型预测结果与现有四元体系实验数据间存在普遍的不一致性,尤其是固溶体形成区域,但模型预测结果从非实验角度给出了重要参考,对现有实验提出了挑战,未来对这些体系开展更为精细的实验研究非常必要。     

Recent Progress on Structure of Aqueous Polyborate Solutions

The crystal structure of metal borates has been extensively investigated by X-ray and neutron diffraction,but,the structure of aqueous polyborate solutions are still largely unknown.Over the last decade,our group has focused on studying the structure of complex aqueous polyborate solutions of Li,Na,K,Rb,Cs,and Mg using synchrotron radiation X-ray scattering(XRS),EXAFS,Raman,NMR,and DFT,as well as determining the density,conductivity and pH of such solutions.Polyborate species distributions were calculated using pH measurements,and the main species in the solution have been confirmed by NMR and Raman spectra.For alkali-metal metaborates,the dominant species is always B(OH)-₄in a wide range of concentration,while the presence of others species is negligible.For alkali metal tetraborates,when concentration is in the extreme low range,only B(OH)₃ and B(OH)-₄ are present in these solutions.As the total boron concentration increases,B(OH)₃ and B(OH)-₄ polycondensated to form more complex oligomers.Of them,while B₄O₅(OH)2-₄ in the tetraborate solutions is the main species,B(OH)₃,B(OH)-₄,and B₃O₃(OH)-₄ are minor species,and B₃O₃(OH)2-₅ and B₅O₆OH)-₄ are present only in negligible amounts.As solution continues to concentrate,B₄O₅(OH)2-₄ eventually becomes the dominant species,which is consistent with the congruent compound M₂B₄O₇·nH₂O(M=Li,Na,K,Rb,Cs) in the system M₂O-B₂O₃-H₂O(M=Li,Na,K,Rb,Cs).For alkali metal pentaborates,B(OH)₃ and B(OH)-₄ are the main species at low concentrations.The species distribution,Raman and NMR spectroscopy results verified that the dominant species in concentrated pentaborate solutions with Li and Na is pentaborate B₅O₆OH)-₄,but it is surprising that the main species with K,Rb,and Cs is always the triborate monoanion B₃O₃(OH)-₄.Although all M[B₅O₆OH)₄]·nH₂O(M=Li,Na,K,Rb,Cs) are all congruent compounds in the system M₂O-B₂O₃-H₂O(M=Li,Na,K,Rb,Cs) ,the main species in aqueous solutions are quite different because of various cation hydration distance(d),hydration number(CN),and configuration,especially charge(Z).For bivalent Mg²⁺,three borate minerals,namely,Inderite(2MgO·3B₂O₃·15H₂O),Hungchaoite(MgO·2B₂O₃·9H₂O),and Mcallisterite(MgO·3B₂O₃·7.5H₂O),exist in the system MgO-B₂O₃-H₂O at 298K.Inderite is a congruent compound,but Hungchaoite and Mcallisterite are incongruent compounds.The species distribution and Raman spectra demonstrat that the predominant species in all the solutions with magnesium borates is bivalent triborate B₃O₃(OH)2-₅,while the subordinate species are B(OH)-₄ at a low B₂O₃/MgO ratio and B(OH)₃at a high B₂O₃/MgO ratio,and the other anions are negligible,as the high Z of the borate anion must match that of Mg²⁺.The disappearance of divalent B₄O₅(OH)2-₄ is in agreement with its incongruent nature.The DFT and XRS results showed that tetrahedral Li(H₂O)⁺₄(d=0.20 nm,CN=4),octahedral Na(H₂O)₆⁺(d=0.236 nm,CN=6),and Mg(H₂O)²⁺₆(d=0.210 nm,CN=6) in the first hydration shell belong to Platonic polyhedra.However,K(H₂O)⁺₈(d=0.28 nm,CN=8,XRS and DFT),Rb(H₂O)⁺₈(d=0.293 nm,CN=7.7-8.2,EXAFS),and Cs(H₂O)⁺₈(d=0.320-0.326 nm,CN=7.6-7.9,EXAFS) are inclined Voronoi polyhedra.Therefore,the effects of cation Z and d on the structure of polyborates in aqueous solutions are deterministic,while the effect of hydrated-cation symmetry is secondary.Their hydrolysis order was:Mg＞Li＞Na＞K＞Rb＞Cs,in step with hydration power.Among them,Mg²⁺ and Li⁺have a strong tendency towards hydrolysis,but Na⁺ scarcely hydrolyzes,especially Rb⁺ and Cs⁺ have a little protonation.X-ray scattering of aqueous alkaline sodium borohydride solutions confirmed that dihydrogen bonds exist in an aqueous solution.The four distinct features of dihydrogen bonds in aqueous solution-unidirectionality,divaricativity,multicentricity,and multidentativity have been also described here in brief.     

Crop water requirements of major crops indryland of northern China

1IntroductionSincetheearlierperiodofthiscentUry,peoplebegantocalculatethecropwaterrequirementSaccordingtotheevaporahonratefromanopenwatersurface,alotofeXPerimentSandresearchesoncropwaterrequirementSandtheirpatternshavebeencAnedoutinmanybranchsciences.Butsofar,theconceptofcropwaterrequirementSstillremainsdiverseandisoftenconfusedwithcropwaterconsumphon.fieldevaporaho4croptTanSpiratioll,andfieldevapoboSPiratioftetc..althoughtheseconceptShavesomesindarihes,theyarenotthesameinfactCropwaterreq…     

山西省中部五大盆地主要作物农田热量、水量盈亏分析

本文根据晋中五大盆地的热量、水量实测数据和当地的实际情况,分析计算了不同耕作制度下主要作物农田热量盈亏量和无灌溉条件下的水量盈亏量。为充分合理利用水热资源,发展农业生产,提供科学依据。     

2000-2015年三江平原主要作物需水量征及影响因素分析

全生育期内作物需水量的研究是农业水资源有效利用和进行合理灌溉的重要依据。基于三江平原22个气象站点2000—2015年逐日气象观测资料及中国区域地面气象要素数据集,利用国际粮农组织 （FAO）Penman-Monteith模型和分段单值平均作物系数法,分别对三江平原水稻、玉米和大豆的作物需水量进行计算,分析作物需水量年际变化特征,采用通径分析法研究作物需水量的变化成因。结果表明：（1）三江平原16 a来年均参考作物蒸散量为537.4 mm,日均为 3.5 mm,呈波动减少趋势。（2）生长季内,水稻在分蘖期需水量最大,为177.1 mm,玉米在七叶期需水量最大,为99.7 mm,大豆在结荚期需水量最大,为96.1 mm;水稻、玉米和大豆的净灌溉需水量分别为195.4 mm、130.8 mm和72.2 mm,对灌溉的依赖程度水稻>玉米>大豆。（3）由通径分析结果可知,三江平原作物需水量的主要影响因素为净辐射、气温和日照时数。     

河北省低平原地区主要作物农田水分盈亏分析

本文计算了河北省低平原地区主要农作物的需水量,根据农田水量平衡方程估算了冬小麦、夏玉米和棉花整个生长期的水分盈亏及其在地区上的差异,分析了作物需水关键期的水分状况。     

滇东北山区坡耕地土壤侵蚀的作物经营因子

通过建立滇东北山区４种代表性作物种植类型———玉米、马铃薯、黄豆、玉米－黄豆间作对降雨引起土壤侵蚀的影响试验小区并进行连续３年实测,分析确定了作物经营因子（Ｃ）值,为建立坡耕地土壤流失方程、进行土壤侵蚀预测预报、制定水土保持农业措施奠定了基础依据     

Variation of fluxes of water vapor, sensible heat and carbon dioxide above winter wheat and maize canopies

Surface energy fluxes were measured using Bowen-Ratio Energy Balance technique (BREB) and eddy correlation system at Luancheng of Hebei Province, on the North China Plain from 1999 to 2001. Average diurnal variation of surface energy fluxes and CO₂ flux for maize showed the inverse “U” type. The average peak fluxes did not appear at noon, but after noon. The average peak CO₂ flux was about 1.65 mg m^-2 s^-1. Crop water use efficiency (WUE) increased quickly in the morning, stabilized after 10:00 and decreased quickly after 15:00 with no evident peak value. The ratio of latent heat flux (λE) to net solar radiation (R_n) was always higher than 70% during winter wheat and maize seasons. The seasonal average ratio of sensible heat flux (H) divided byR _n stayed at about 15% above the field surface; the seasonal average ratio of conductive heat flux (G) divided by R_n varied between 5% and 13%, and the averageG/R> _n from the wheat canopy was evidently higher than that from the maize canopy. The evaporative fraction (EF) is correlated to the Bowen ratio in a reverse function.EF for winter wheat increased quickly during that revival stage, after the stage, it gradually stabilized to 1.0, and fluctuated around 1.0. EF for maize also fluctuated around 1.0 before the later grain filling stage, and decreased after that stage.     

山西省大同市农业生态气候适宜度评价

文章选择黄土高原边缘,颇具生态地理意义的山西省大同市及所辖7个县区为研究对象,依据该区域1971~2000年的长期实测气象资料,在借鉴前人建立的农业生态气候适宜度动态模型的基础上,经过多次作物实验,尝试性拟合出符合区域特点的典型气候要素适宜度隶属函数;分区计算了农业生态资源指数 、效能指数及利用系数,总结出区域气温及降水量适宜度曲线大致呈 "∩"型分布规律,峰值出现在每年的6~8月之间;日照百分率适宜度曲线呈 "∪"型分布规律,谷值出现在每年的7月。在SPSS统计软件环境中,以各区域累年逐月平均效能指数为分类实体,进行模糊动态聚类,提出研究区农业生态气候适宜度的三种等级模式。     

The differences of water balance components of Caragana korshinkii grown in homogeneous and layered soils in the desert–Loess Plateau transition zone

Soil texture greatly influences soil water movement, thus may affect the water balance and vegetation growth in the desert–Loess Plateau transition zone. This study is to determine if the water balance differs in homogeneous and layered soils with Caragana korshinkii stands in semiarid region. Soil water measurements up to 500-cm depth were taken in 2006 and 2007 on homogeneous sandy soil, homogeneous silt loam soil, and layered soil with sand overlying silt loam. HYDRUS-1D was used to simulate the soil water balance. The results indicated the annual water balance components were greatly affected by soil layering. The ratio of average actual evapotranspiration (ET_a) to precipitation (P) during the two years in the layered soil was slightly lower than that in homogeneous soils. The ratios of annual actual transpiration (T_r) to evapotranspiration were 50.9%, 41.2% and 30.6% in layered soil, homogeneous sandy soil, and homogeneous silt loam soil, respectively. C. korshinkii grown in layered soil had deeper soil water recharge and higher T_r/ET_a ratio, thus had more available water for transpiration than that in homogeneous soils. This study suggested the layered soil with sand overlying silt loam is more favorable to C. korshinkii growth in terms of water use than homogeneous soils in the desert–Loess Plateau transition zone.     

ASSESSING THE SUITABILITY OF THE EPIC CROP MODEL FOR USE IN THE STUDY OF IMPACTS OF CLIMATE VARIABILITY AND CLIMATE CHANGE IN WEST AFRICA

The EPIC (Erosion Productivity Impact Calculator) crop model, developed by scientists of the United States Department of Agriculture (USDA), has been successfully applied to the study of erosion, water pollution, crop growth and production in the US but is yet to be introduced for serious research purposes in other countries or regions. This paper reports on the applicability of the EPIC 8120 crop model for the assessment of the potential impacts of climate variability and climate change on crop productivity in sub‐Saharan West Africa, using Nigeria as the case study. Among the crops whose productivity has been successfully simulated with this model are five of West Africa's staple food crops: maize, millet, sorghum (guinea corn), rice and cassava. Thus, using the model, the sensitivities of maize, sorghum and millet to seasonal rainfall were demonstrated with coefficients of correlation significant at over 98 per cent confidence limits. The validation tests were based on a comparison of the observed and the model‐generated yields of rice and maize. The main problems of validation relate to the multiplicity of crop varieties with contrasting performances under similar field conditions. There are also the difficulties in representing micro‐environments in the model. Thus, some gaps appear between the observed and the simulated yields, arising from data or model deficiencies, or both. Based on the results of the sensitivity and validation tests, the EPIC crop model could be satisfactorily employed in assessing the impacts of and adaptations to climate variability and climate change. Its use for the estimation of production and the assessment of vulnerabilities need to be pursued with further field surveys and field experimentation.     

基于MODIS NDVI的西辽河流域主要粮食作物时空分布格局

研究以西辽河流域为案例区,以MODIS遥感数据为基础,选取2000、2005和2010年时间点,利用NDVI时间序列信息,结合西辽河流域不同作物物候历,运用决策树提取模型,获取西辽河流域春玉米、春小麦和大豆等主要作物的空间分布信息,定量揭示了10年间西辽河流域主要粮食作物的时空分布特征。研究表明：（1）2010年西辽河流域主要粮食作物播种面积为11 965.08 km2,其中春玉米播种面积约占流域主要粮食作物的92.28%,集中在西辽河流域下游地区;春小麦播种面积占比3.14%,以西辽河流域中游面积最大;大豆播种面积占比4.58%,以西辽河上游流域面积最大。（2）2000-2005年西辽河流域主要粮食作物播种面积大幅增加,涨幅达29.77%,集中在西辽河流域下游地区。其中,春玉米播种面积增长38.99%,春小麦播种面积减少39.04%,大豆播种面积增长21.27%。（3）2005-2010年西辽河流域主要粮食作物播种面积增长缓慢,涨幅为5.18%,集中在西辽河流域下游地区。春玉米播种面积呈现增加趋势,春小麦呈现减少趋势,大豆呈减少趋势。