EDXRF测定土壤元素含量及其在有机碳垂直分布特征研究中的应用

针对X射线荧光光谱(XRF)法不确定度计算和测定地质样品中硫的准确度、精密度与可靠性不高的难点,研究了提高土壤中硫分析准确度的途径,建立了土壤中S的XRF分析方法,完善了偏振能量色散XRF测定土壤中主、次、痕量元素的方法,利用不确定度评价、证实了所见方法的有效性和可靠性。测定、获得了研究区土壤元素剖面,通过对短期植被更替土壤剖面的土壤有机碳含量(TOC)、有机碳稳定碳同位素((13C)特征及其与元素垂直分布的关系研究,发现土壤中元素含量与有机碳含量和有机碳稳定碳同位素存在显著相关性。     

X射线荧光光谱及拉曼光谱法研究五谷营养成分

采用X射线荧光光谱分析法(XRF)和激光拉曼光谱法(Raman),测定了小米、玉米、黄米、大米和小麦5种常用主食(五谷)中营养成分及钾、镁、钙、铁、锌、锰、铝、铜等多种微量元紊的含量.X射线荧光光谱分析法测量结果表明,五谷中所含微量元素非常丰富且种类基本相同,但各元素含量存在很大差异.5种谷类中K元素含量均为最高,含量...     

地球化学样品中有机碳的光谱分析

有机碳已成为多目标地球化学调查、土地质量地球化学调查等项目研究的必测指标,对有机碳的准确定量是地球化学调查工作的重要内容,准确测定有机碳含量具有重要意义。然而传统的重量法、容量法流程长、速度慢,已经不能满足大批量及快速测定地球化学样品的要求。采用稀盐酸去除样品中的无机碳,应用高频红外碳硫分析仪对不同类型地球化学样品中有机碳的测定进行了研究,着重从称样量、酸的选择、最佳浓度及用量、助熔剂的选择和最佳加入量进行对比实验,优化出适合分析地球化学样品中有机碳含量的条件,并采用国家一级地球化学标准物质建立校准曲线,建立盐酸预处理-红外吸收光谱法测定地球化学样品中有机碳含量的分析方法。结果表明：陶瓷坩埚经1 200 ℃灼烧处理可以有效降低碳空白,减小对分析结果的影响;选择50.0～70.0 mg称样量,测试准确度高且样品熔融时不易喷溅;0.40～0.60 mL稀盐酸（1+7）除尽样品中的无机碳同时减少有机碳流失损失;0.40～0.50 g纯铁屑和1.50～1.70 g钨粒作为助熔剂,助熔效果稳定;采用国家一级地球化学标准物质建立校准曲线,校准曲线线性良好（R2=0.998 5）。该方法的检出限为69 μg·g-1,测定结果的相对标准偏差（RSD,n=12）均小于8%。经63个不同类型国家一级地球化学标准物质（土壤、岩石、水系沉积物）验证,测定结果与标准值相符。本方法操作简便,检出限低,灵敏度高,结果准确可靠,适用于地球化学样品中有机碳含量的测定。     

NMR法测定重油中碳、氢的质量百分含量

用高分辨的1H-NMR和13C-NMR法对重油中的氢、碳的质量百分含量进行测定.采用标准化合物考察了本方法的准确性,以实际油样考察了方法的重复性,则本方法具有良好的准确性、重复性.然后测定了30个重油油样的氢、碳的质量百分含量,测定结果与元素分析法(ASTM D5291)有很好的一致性.核磁共振法可以用于测定重油中碳、氢含量.     

火焰原子吸收光谱法测定粮食中锌的含量

用硝酸和高氯酸消解试样,用火焰原子吸收光谱法测定几种谷物小米、黑米、薏米和玉米中锌元素含量.试验结果表明方法简便、快速、准确.回收率:91.3%-100.0%.     

近红外光谱法非破坏性测定黄豆籽粒中蛋白质、脂肪含量

采用傅里叶近红外漫反射光谱非破坏性分析 ,能够提供完整籽粒黄豆样品成分的含量信息 ,结合偏最小二乘回归法 (PartialLeast Squares,PLS) ,以 39个不同品种的完整籽粒黄豆样品建立蛋白质和脂肪含量近红外定量分析模型 ,其中蛋白质、脂肪含量分析模型的测定系数R2 分别为 99 30 ,97 5 2 ,相对标准偏差RSD分别为 0 76 %和 1 3% ,检验集的化学值与模型预测值的相关系数r分别为 0 94 73,0 86 95。用所建模型对 2 6 4个不同品种的黄豆样品进行预测 ,并采用R error指标来估计分析结果的误差 ,其中蛋白质和脂肪模型预测的最小相对误差分别为 0 0 4 %和 2 4 6 % ,最大相对误差分别为 2 4 5 %和 4 2 5 %。该结果对育种过程中的早代筛选工作有重要意义     

不同培肥土壤颗粒有机碳的~(13)C核磁共振与红外光谱对比分析（英文）

为明确颗粒有机碳在土壤固碳中的作用机制,对比研究了不同有机培肥土壤颗粒有机碳的结构差异。以单施化肥处理为对照,选择了四种有机物料进行定位培肥试验,利用~(13) C NMR和红外光谱技术对比分析不同有机培肥对土壤颗粒有机碳结构的影响。结果表明:颗粒有机碳以脂肪碳和含氧基团为主,脂化度高于75%,含氧官能团含量高于50%;不同有机培肥对土壤颗粒有机碳结构的影响差异性显著,树叶培肥在提高颗粒有机碳芳香度的同时,亲水性也大幅度提高,比单施化肥处理(对照)提高了0.78%;短期内,牛粪、秸秆和树叶培肥均可提高土壤颗粒有机碳的芳香度,但从长远角度分析,牛粪和秸秆培肥更利于土壤颗粒有机碳的稳定,尤其是秸秆培肥,其颗粒有机碳的芳香度分别比对照和牛粪培肥高0.35%和0.11%,而亲水性远低于二者;红外光谱与核磁分析的结果基本一致,红外光谱可用于大量样品的颗粒有机碳结构初步筛选。     

不同培肥土壤颗粒有机碳的13C核磁共振与红外光谱对比分析

为明确颗粒有机碳在土壤固碳中的作用机制,对比研究了不同有机培肥土壤颗粒有机碳的结构差异。以单施化肥处理为对照,选择了四种有机物料进行定位培肥试验,利用13C NMR和红外光谱技术对比分析不同有机培肥对土壤颗粒有机碳结构的影响。结果表明：颗粒有机碳以脂肪碳和含氧基团为主,脂化度高于75%,含氧官能团含量高于50%;不同有机培肥对土壤颗粒有机碳结构的影响差异性显著,树叶培肥在提高颗粒有机碳芳香度的同时,亲水性也大幅度提高,比单施化肥处理(对照)提高了0.78%;短期内,牛粪、秸秆和树叶培肥均可提高土壤颗粒有机碳的芳香度,但从长远角度分析,牛粪和秸秆培肥更利于土壤颗粒有机碳的稳定,尤其是秸秆培肥,其颗粒有机碳的芳香度分别比对照和牛粪培肥高0.35%和0.11%,而亲水性远低于二者;红外光谱与核磁分析的结果基本一致,红外光谱可用于大量样品的颗粒有机碳结构初步筛选。     

长期不同施肥处理对黑土根际土壤有机碳结构组分的影响

土壤有机碳是农业生态系统的关键驱动和调节者,特别是根际微域有机碳动态对土壤碳素循环和矿质营养元素释放起着重要作用。研究长期不同化肥和有机肥施用下大豆根际土壤有机碳、活性有机碳以及有机碳结构的变化规律,深入了解根际有机碳固持和稳定机制,为完善农田生态系统碳固持和农田可持续发展提供科学依据和理论支撑。该研究依托黑土长期定位试验,采用化学分析、固态13C-核磁共振 (13C-NMR)等方法研究大豆根际土壤有机碳含量、活性有机碳含量和有机碳结构组分变化规律。结果表明,与非根际土壤相比,大豆根际土壤有机碳含量显著增加,长期施肥处理能够显著增加根际土壤有机碳和低活性有机碳含量,以常量有机肥加氮磷钾（MNPK）处理提升效果最好。核磁共振实验结果表明,与不施肥处理相比,MNPK处理明显增加根际土壤烷基碳、烷氧基碳比例以及烷基碳/烷氧基碳比值,降低芳香基碳和芳香碳/总碳比值,在非根际土壤中尤其显著;常量氮磷钾（NPK）处理增加芳香基碳比例和芳香碳/总碳比值,在根际土壤中烷基碳比例和烷基碳/烷氧基碳比值增加,烷氧基碳比例降低,非根际土壤测试结果相反。综上所述,MNPK处理能够显著提升根际有机碳含量,增加有机碳中烷基碳、烷氧基碳比例以及烷基碳/烷氧基碳比值,促进团聚体形成和增加土粒结构稳定性,而NPK处理增加芳香基碳比例和芳香碳/总碳比值,降低根际烷氧基碳比例,团聚体稳定性降低,同时证明固态13C-核磁共振技术结合半定量分析能够准确地分析不同有机碳结构组分变化,深刻认识根际土壤有机碳的稳定机制。     

非色散红外吸收法测定地表水和废水中的总有机碳

用燃烧氧化 -非色散红外吸收法测定了杭州市辖区内的地表水、污水处理厂排水和不同行业工业废水中的总有机碳 (TOC)。结果表明 ,本法检出限为 0 .3mg/ L ,对于 TOC浓度在 6 .1— 12 0 mg/ L范围内水样的测定 ,相对标准偏差在 1.3%— 10 %之间。     

自然老化谷类种子的二维红外光谱研究

种粮老化影响种子活力及粮食品质。利用傅里叶变换红外光谱(FT-IR),二阶导数红外光谱(SD-IR)和二维相关红外光谱(2D-IR)方法对不同储藏年份的大麦,小麦,稻谷,玉米和高粱种子进行区分研究。结果显示,原始光谱中几个峰强比有差异;在二阶导数红外光谱中,不同储藏年份种子在1 800～800 cm-1范围内的吸收峰强度和形状显示出差异。二维相关红外光谱结果显示：大麦在1 350～1 800 cm-1,小麦,稻谷,玉米和高粱在860～1 690 cm-1范围内有明显差异,随储藏年份增加,自动峰和交叉峰的数目减少,强度减弱。结果表明,应用傅里叶变换红外光谱结合二维相关红外光谱能有效快速地区分不同储藏年份的谷类种子。     

Partitioning of atmospheric carbon dioxide over Central Europe: insights from combined measurements of CO2 mixing ratios and their carbon isotope composition

Regular measurements of atmospheric CO (2) mixing ratios and their carbon isotope composition ((13)C/(12)C and (14)C/(12)C ratios) performed between 2005 and 2009 at two sites of contrasting characteristics (Krakow and the remote mountain site Kasprowy Wierch) located in southern Poland were used to derive fossil fuel-related and biogenic contributions to the total CO (2) load measured at both sites. Carbon dioxide present in the atmosphere, not coming from fossil fuel and biogenic sources, was considered 'background' CO (2). In Krakow, the average contribution of fossil fuel CO (2) was approximately 3.4%. The biogenic component was of the same magnitude. Both components revealed a distinct seasonality, with the fossil fuel component reaching maximum values during winter months and the biogenic component shifted in phase by approximately 6 months. The partitioning of the local CO (2) budget for the Kasprowy Wierch site revealed large differences in the derived components: the fossil fuel component was approximately five times lower than that derived for Krakow, whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighbourhood of the station. While the presented study has demonstrated the strength of combined measurements of CO (2) mixing ratios and their carbon isotope signature as efficient tools for elucidating the partitioning of local atmospheric CO (2) loads, it also showed the important role of the land cover and the presence of the soil in the footprint of the measurement location, which control the net biogenic surface CO (2) fluxes.     

Studies of sound transmission in various types of stored grain for acoustic detection of insects

In developing passive acoustic systems for detecting insect infestations in bulk-stored grain, it is advantageous to understand the transmission of sound in the grain between the insects and the sensors. In the work presented here grain is shown to be a strong acoustical absorber, the attenuation coefficient increasing roughly as the square root of the frequency. Tests with soft wheat immersed in three different gases: air, argon and carbon dioxide, support an earlier conclusion that sound is transmitted principally through the gas in the passageways between the grain kernels. The speed of sound and the attenuation coefficient were measured as a function of frequency for six different types of grain: hard and soft wheat, brown rice, soybeans, corn and sorghum. It was determined that sound is transmitted over longer distances in grains with a larger inter-kernel spacing, such as corn and soybeans. Grain depth, up to several meters, appears to have little effect on sound transmission.     

氯原子引发的甲基过氧化氢大气光化学反应

有机过氧化物在大气化学过程中起着重要作用 ,并对城市大气质量有着重要影响 ,然而 ,目前对它们大气化学行为的了解还非常不够 ,尤其缺少定量的研究。文章利用长光路傅里叶变换红外光谱 (长光路FTIR)仪原位跟踪反应进程 ,进行实验室模拟研究大气中非常重要的一种有机过氧化物 ,即甲基过氧化氢(CH3OOH ,MHP)的大气光化学反应。反应在内配有红外光多次反射镜 (White镜 )的 2 8 5L静态石英反应池中进行 ,采用氯原子 (Cl)引发反应 ,温度为 (2 92± 2 )K ,压力为 9 3× 10 4 Pa(2 0 %O2 80 %N2 )。FTIR光谱表明反应产物中主要包括甲醛 (HCHO)、甲酸 (HCOOH)、一氧化碳 (CO)和二氧化碳 (CO2 ) ,此外还有少量的甲醇 (CH3OH)生成。测定了前三种主要产物在反应 6 0min内的产率 :HCOOH和CO产率分别为 2 4 %和 6 % ;而HCHO浓度先增后减 ,浓度达到峰值时产率为 5 0 %。根据实验结果探讨了可能的反应机理 ,指出MHP是大气中HOx 自由基的储库分子 ,对整个大气光化学反应的进程有重要作用     

Partitioning of atmospheric carbon dioxide over Central Europe: insights from combined measurements of CO 2 mixing ratios and their carbon isotope composition

Regular measurements of atmospheric CO ₂ mixing ratios and their carbon isotope composition (¹³C/¹²C and ¹⁴C/¹²C ratios) performed between 2005 and 2009 at two sites of contrasting characteristics (Krakow and the remote mountain site Kasprowy Wierch) located in southern Poland were used to derive fossil fuel-related and biogenic contributions to the total CO ₂ load measured at both sites. Carbon dioxide present in the atmosphere, not coming from fossil fuel and biogenic sources, was considered ‘background’ CO ₂. In Krakow, the average contribution of fossil fuel CO ₂ was approximately 3.4%. The biogenic component was of the same magnitude. Both components revealed a distinct seasonality, with the fossil fuel component reaching maximum values during winter months and the biogenic component shifted in phase by approximately 6 months. The partitioning of the local CO ₂ budget for the Kasprowy Wierch site revealed large differences in the derived components: the fossil fuel component was approximately five times lower than that derived for Krakow, whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighbourhood of the station. While the presented study has demonstrated the strength of combined measurements of CO ₂ mixing ratios and their carbon isotope signature as efficient tools for elucidating the partitioning of local atmospheric CO ₂ loads, it also showed the important role of the land cover and the presence of the soil in the footprint of the measurement location, which control the net biogenic surface CO ₂ fluxes.     

直射太阳光红外吸收光谱技术遥测大气中二氧化碳柱浓度

大气中二氧化碳浓度持续增高导致环境和气候变化等问题成为人们关注的焦点. 为了实时遥测二氧化碳气体柱浓度, 研究了一种地基低分辨遥测系统和实时光谱数据反演分析方法. 利用该系统在合肥地区进行了连续观测, 从太阳吸收光谱中实时获取了整层大气透过率. 采用逐线积分非线性最小二乘光谱反演算法, 从整层大气透过率中反演了二氧化碳柱浓度和氧气柱浓度, 并以氧气柱浓度为内标函数获得了二氧化碳干空气柱体积混合比, 精密度优于3%. 将2012年9月25日12时到15时本系统测量的二氧化碳干空气柱体积混合比均值与此时段过境本站点区域的日本温室气体卫星观测结果进行了比较, 两者偏差小于1%.可见, 该系统和方法具有很高的精密度和准确度, 是一种有效的温室气体观测手段. 关键词： 红外吸收光谱技术 遥测 二氧化碳 柱浓度     

Sonochemical reduction of carbon dioxide

Sonolysis of carbon dioxide dissolved in water was performed from a standpoint of reducing this material in atmosphere. During one hour of sonication, the amount of CO2 decreased to about half at 5 degrees C under CO2-Ar atmosphere. The decreasing rate for CO2 followed the order Ar > He > H2 > N2 and it was down with increasing temperature in the range of 5-45 degrees C. The most favorable concentration for reducing CO2 was 0.03 (mole fraction of CO2 in gas phase). This concentration in gas phase means an equal mixture of CO2 and Ar in water, because CO2 is more soluble than Ar. Since carbon dioxide dissolved in water would be partly ionized, the roles of ions on the sonolysis were also examined. Gaseous reaction products were CO, H2 and a small amount of O2. Carbon monoxide and hydrogen might be obtained from CO2 and H2O by sonolysis, respectively. Both gases are fuel and react each other to C1 compounds such as methanol, and so on. Therefore, irradiation of ultrasonic waves should be an important technique for reducing CO2.     

Diurnal variability of delta13C and delta18O of atmospheric CO2 in the urban atmosphere of Kraków, Poland

This article presents the results of measurements of the isotopic composition and concentration of atmospheric carbon dioxide, performed on air samples from Kraków (Southern Poland) in different seasons of the year. A simple isotope mass balance model has been applied to determine the contributions of different sources of CO2 to the urban atmosphere of Kraków city: the latitudinal/regional background, biospheric contributions and anthropogenic emissions. The calculations show that during the summer and early autumn the dominant contribution to local CO2 peaks is the biosphere, making up to 20% of atmospheric CO2 during the nocturnal temperature inversion in the lower troposphere. During early spring and winter, anthropogenic emissions are the main local source.     

大气压非平衡等离子体甲烷干法重整零维数值模拟

大气压非平衡等离子体由于其独特的非平衡特性,可为甲烷和二氧化碳稳定温室气体分子活化和重整提供非热平衡和活化环境.本文采用了零维等离子体化学反应动力学模型,考虑了详细的CH₄/CO₂等离子体化学反应集,重点研究了反应气体CH₄/CO₂摩尔分数(5%—95%)对大气压非平衡等离子体甲烷干法重整制合成气和重要含氧化合物的影响.首先,给出了进料气体不同体积比时电子密度和温度随时间的演化规律,结果表明初始甲烷摩尔分数的提高有利于获得较高的电子密度和电子温度.随后,讨论了主要自由基和离子数密度在不同的甲烷摩尔分数下随着时间的变化规律,并给出了反应气体的转化率、合成气体和重要含氧化合物的选择性.此外,还明确了合成气和含氧化合物主要生成和损耗的化学反应路径,发现甲基和羟基是合成含氧化合物的关键中间体.最后,归纳总结给出了主要等离子体粒子之间的总体等离子体化学反应流程图.