二阶导数光谱法快速测定硝酸盐氮和亚硝酸盐氮

紫外吸收方法中，硝酸盐氮(NO-₃-N)的紫外吸收峰在202.0 nm左右，而亚硝酸盐氮(NO-₂-N)的紫外吸收峰在210.0 nm左右，两者吸收峰位置距离很近，因此，在分析过程中两者的紫外吸收曲线严重重叠，相互之间严重干扰，不经过分离很难用单波长对二者的含量进行测定而常用的国标方法过程又过于繁琐，耗时较长。为了准确、快速、环保的实现环境水体和饮用水中的硝酸盐氮和亚硝酸盐氮快速监测，避免国标方法中对二者测定的诸多不足，结合紫外吸收和二阶导数光谱法，在不经过任何预先分离处理的情况下，建立了水体中这两种物质的快速分析方法，实现水样中二者的快速准确测定。研究采用优级纯试剂配制硝酸盐氮和亚硝酸盐氮系列标准溶液。以去离子水做参比，采用紫外-可见光分光光度计扫描其在195～250 nm范围内的紫外吸收光谱，之后采用Origin软件对所获得的光谱图做二阶导数处理，并采用Origin软件中的Savitzky-Golay方法对处理后的二阶导数光谱进行平滑处理以去除其他无关的干扰和噪声。通过观察上述所得两组二阶导数光谱图，得出以下结论，不同浓度的亚硝酸盐氮样品在223.5 nm处吸光度的二阶导数均为0，不同浓度的硝酸盐氮样品在216.5 nm处的吸光度的二阶导数也均为0。通过实验可见硝酸盐氮和亚硝酸盐氮混合样品的紫外吸收光谱的二阶导数在这两个特定波长处符合朗伯比尔定律。实验通过配制硝酸盐氮和亚硝酸盐氮混合样品，并扫描混合样品的紫外吸收光谱，采用上述方法对所得光谱做二阶导数及平滑去噪处理。研究混合样品二阶导数光谱图可以看出在硝酸盐氮浓度相同而亚硝酸盐氮浓度不同时，亚硝酸盐氮的浓度变化会对硝酸盐氮的吸光度的二阶导数有影响，但是各种混合样品的二阶导数光谱在223.5 nm处几乎交叉于一点，说明此处亚硝酸盐氮的浓度不同不会对硝酸盐氮的二阶导数吸光度有影响。且在223.5 nm处硝酸盐氮二阶导数吸光度随浓度增加而线性增加。因此，223.5 nm可作为混合组分中硝酸盐氮的测定波长。参照以上方法，可得亚硝酸盐氮的测定波长为216.5 nm。在223.5 nm处对单组分的硝酸盐氮的浓度值及其相应的吸光度的二阶导数进行线性回归，其线性关系良好，得到标准曲线的回归方程为C=438.69A+0.015，R2=0.995 9。同理，得到亚硝酸盐氮在216.5 nm处回归方程为C=-657.29A+0.068 8，R2=0.998。为了验证这种方法在实际水样测量中能否成立，取秦皇岛市新河、汤河以及戴河三种河水水样进行实验验证，结果表明，回收率在96.7%～103.0%之间，相对标准偏差在1.46～3.68之间。该方法结果较准确，且操作更加简便，成本较低，可同时实现硝酸盐氮和亚硝酸盐氮快速在线监测。     

双波长法快速测定饮用水中的硝酸盐氮和亚硝酸盐氮

针对快速性要求较高的场合,提出基于双波长法测定硝酸盐氮和亚硝酸盐氮含量的方法,该法首先测定混合溶液在203、216、220nm处的吸光度值,其次计算216nm与203nm处的吸光度差值,通过差值的线性回归方程计算出硝酸盐氮的浓度,再通过亚硝酸盐溶液的校准曲线计算亚硝酸盐氮的含量。通过实验和分析计算,可知此法原理简单,使用方便,精密度和准确度较高,而且在没有分光光度计的情况下也能使用,大大提高了分析效率,适合用在快速估算硝酸盐氮和亚硝酸盐氮含量的场合。     

The Impact of Ozone on the 15N Incorporation and Nitrogen Assimilation of Wheat and Maize

Abstract

Young wheat (C3) and maize (C4) plants were exposed to near-ambient concentrations of ozone in open-top chambers in order to investigate the possible effects of ozone on nitrogen metabolism. Nitrogen was supplied to the plants by adding ¹⁵N-labelled tracer substances via the soil substrate. Enzyme activities (NADH nitrate reductase, nitrite reductase, glutamine synthetase and NADH glutamate dehydrogenase) and the incorporation of ¹⁵N were determined.

The findings show that nitrogen metabolism was affected by O₃, however, there were distinct differences between the two species. In plants treated with O₃, NADH nitrate reductase activity in maize leaves was reduced, while NR activity in wheat leaves only slightly declined. Only minor changes were observed with respect to the activities of nitrite reductase, glutamine synthetase and NADH glutamate dehydrogenase.

Feeding experiments using ¹⁵NO₃ ^? showed that the incorporation of nitrate nitrogen in wheat plants exposed to ozone remains virtually unchanged, whereas in maize plants reduced incorporation rates were observed for nitrate nitrogen. The incorporation of ammonium nitrogen was distinctly increased in wheat and maize by the impact of ozone.

When investigating pigment contents, reduced levels of chlorophyll a and b and carotenoids were observed, whereas the pigment content of wheat leaves remained unchanged. These results indicate that young maize plants are more susceptible than wheat plants to short-term ozone exposure.     

主成分分析结合BP神经网络对短程生物脱氮中氮的近红外光谱研究

为实现高效短程生物脱氮及氨氮和亚硝酸盐氮的快速检测,采用主成分分析结合BP神经网络的方法建立短程生物脱氮工艺中氨氮和亚硝酸盐氮的近红外光谱定量分析模型(BP神经网络模型)。工艺运行结果表明：原水经过好氧阶段氨氮从45.3 mg·L-1下降到2.7 mg·L-1,亚硝酸盐氮从0.01 mg·L-1上升到19.6 mg·L-1,硝酸盐氮受到抑制;在缺氧段亚硝酸盐氮从19.6 mg·L-1下降至1.2 mg·L-1,系统实现了良好的短程生物脱氮效果。水样原始光谱主成分分析表明：前13个主成分代表了原始光谱数据的信息,其累计贡献率达到95.04%,排除了冗余信息且大大降低了模型的维数,光谱数据矩阵从192×2 203减少到192×13,大大降低了运算量并提高了模型的精度。BP神经网络模型校正结果显示：BP神经网络模型对氨氮、亚硝酸盐氮校正时的决定系数(R2)分别达到0.950 4和0.976 2,校正均方根误差(RMSECV)分别为0.016 6和0.010 9。BP神经网络模型预测结果显示：BP神经网络模型对氨氮、亚硝酸盐氮预测输出与期望输出之间的决定系数(R2)分别为0.974 0和0.981 4,预测均方根误差(RMSEP)分别为0.033 7和0.028 7,模型预测效果良好。研究表明,BP神经网络模型可以通过快速测定水样的近红外光谱数据预测短程生物脱氮工艺中氨氮和亚硝酸盐氮浓度,并根据氨氮和亚硝酸盐氮浓度变化及时、灵活地控制工艺的运行,为生物脱氮提供快速有效的检测技术和科学依据。     

流动注射在线消解测定水中总氮

研究了流动注射在线消解测定水中总氮的自动分析方法。方法基于使用电热和紫外在碱性过硫酸钾体系中消解样品,有机形态和无机形态的氮都被氧化为硝酸盐氮,消解效率为93.0%—108.5%。硝酸盐通过镀铜的镉柱还原为亚硝酸盐,亚硝酸盐与4-对氨基苯磺酰胺、N-（1-萘基）乙二胺盐酸盐形成偶氮染料,在540nm处进行测定。方法的线性范围为20.0—2000.0μg.L-1（r≥0.9995）,检出限为8.3μg.L-1,相对标准偏差为0.8%—1.6%;样品测定频率为35样/h,地表水、地下水、自来水等实际水样的加标回收率为95.9%—107.3%。对于污水样品中的总氮测定FIA与国标方法GB 11894-89对比,无显著差异。     

河水中亚硝酸盐氮的生物降解

通过分光光度法测定了亚硝酸盐氮的含量,并从培养条件优化和游离氨抑制作用两方面考察了河底活性淤泥对水体中亚硝酸盐氮的生物降解情况;在最佳条件下,河水中亚硝酸盐氮的降解在2天内降解率可达83.7%.     

Nitrogen retention in the Szczecin Lagoon,Baltic Sea

Nitrogen (N) retention and transformation in the Szczecin Lagoon, southern Baltic Sea, were studied by means of budget calculations and stable isotope data of dissolved and particulate matter. Two stations, one located at the main outlet of the lagoon (?wina Strait) and the other 100 km to the south, on the Oder River (Widuchowa), were sampled biweekly over the years 2000–2002. The Oder River is one of the five largest rivers draining into the Baltic Sea and the largest one discharging its waters into the western Baltic. According to our data, the Oder River carried approximately 60 kt y^?1 total N, of which 7 kt y^?1 (<12 %) are particulate organic nitrogen and 46 kt y^?1 (77 %) dissolved inorganic nitrogen. Seasonal patterns of particulate nitrogen and nitrate concentrations were similar at Widuchowa and ?wina Strait station, but nitrate concentrations in the ?wina Strait were much lower, pointing not only to the dilution effect but also to considerable nutrient removal capacity (especially of nitrate) in the lagoon. The loss of nitrate suggests that denitrification is the major N-removal process, whereas primary production was only a minor contributor, due to the very low particle load. Combining budget calculations with stable isotope measurements reveal unique information about nitrogen turnover processes in the lagoon.     

顺序注射-连续光谱测定水质多参数方法研究

针对水质多参数监测仪器的低功耗、微型化、集成化和智能化,研制了一种基于顺序注射分析技术（SIA）和连续光谱检测方法融合的微型测定原位水质多参数检测仪,系统设计的核心在于消解池结构设计且消解池作为检测池,以及微控技术顺序注射平台的原理设计和多参数联合消解测定流程设计。对融合SIA和连续光谱水质多参数原位分析的新方法进行实验研究。设计了基于国标水质检测标准的多参数顺序注射分析检测流程,基于分光光度检测方法,在使用连续光谱扫描测量的条件下,融合顺序注射分析技术对亚硝酸盐氮、硝酸盐氮、总氮、总磷的含量进行检测。测定消解前,对硝酸盐氮、亚硝酸盐氮进行直接光谱测量,测定消解后对总氮进行光谱检测,显色反应后,对总磷进行光谱检测。在本系统下,以亚硝酸盐氮、硝酸盐氮、总磷和总氮原位水质参数为测定对象,基于连续光谱分析,最小二乘法建立回归模型并绘制各参数的浓度-吸光度标准工作曲线,其拟合优度（即决定系数）≥0.989 9。配制已知亚硝酸盐氮、硝酸盐氮、总氮、总磷含量的混合溶液,按照上述的多参数检测流程,利用本系统绘制出的标准工作曲线测量4个参数,实验结果表明,实验参数重复性（相对标准偏差）RSD≤3.86%,系统可稳定、高效的分析不同水样中的亚硝酸盐氮、硝酸盐氮、总氮、总磷含量。基于SIA-连续光谱融合测定原位水质多参数检测方法研究,对于提升在线水质监测仪器的技术性能具有重要作用,微型多参数水质监测仪的研制具有良好的参数扩展前景,适用于多种水质在线监测平台。     

Separation of Ammonium and Nitrate for Isotopic Analysis of Nitrogen 15 Using Vacuum Distillation Method

The parameters affecting the vacuum distillation method for quantitative separation of ammonium and nitrate for mass spectrometric determination of ¹⁵N were investigated. The vacuum distillation was found to be advantageous to steam distillation method because no interference from organic compounds was encountered, greater volumes could be processed and no previous evaporation of the water samples was necessary. The mass spectrometric isotopic analysis of nitrogen 15 proved the suitability of the vacuum distillation method for quantitative separation of ammonium and nitrate.     

Aufnahme von 15NO2 und Einbau des 15NO2-Stickstoffs in verschiedene Stickstofffraktionen bei Sonnenblumen (Uptake of 15NO2 and Metabolic Transfer of the 15NO2 Nitrogen to Various Nitrogen Fractions of Sunflowers)

Abstract

Sunflowers were exposed to ¹⁵NO₂ at a range between 4,9 and 42,0 ppb. The ¹⁵NO₂ uptake was quantified and the fate of the ¹⁵N in different parts and pools of nitrogen was investigated. The very high δ¹⁵N-values of the free amino acid pool can't give an answer to the question whether the NO₂-nitrogen is incorporated by a different pathway, compared to the nitrogen which derives from root uptake. Or does a compartmentation of the nitrate pool in the plant cell cause a dilution of the ¹⁵N enrichment in the mineral nitrogen pool during sample preparation?     

植物中硝态氮、氨态氮、总氮测定方法的比较研究

植物样品经硫酸 过氧化氢凯氏法消煮后 ,分别用直接吸光光度法、靛酚蓝比色法、过硫酸钾氧化吸光光度法获得硝态氮 (包括亚硝态氮 )、氨态氮、总氮的含量。通过样品测试数据的比较 ,证明分别测得的氨态氮、硝态氮含量之和与所测总氮结果一致。本文为植物生态学和植物学中氮元素各种形态含量的分析提供了选择测定方法的依据     

水中亚硝酸盐氮测定条件优化

采用紫外分光光度法对嘉陵江水中亚硝酸盐氮的含量进行定量分析。优化测定条件,得最佳测定条件为：氢氧化锌处理水样,1g/L碱性品红2.00mL,反应时间20min。测得水样中亚硝酸盐氮平均含量为2.875mg/L。该方法试剂无毒,操作简便快捷,干扰小,适合水质中亚硝酸盐氮的定量分析。     

机器学习在紫外法测定硝酸盐氮浓度中的应用

紫外分光光度法(UV法)由于较传统化学方法具有效率高操作简便、无二次污染且可现场原位测试等优点,近些年来被广泛应用到水质参数的测试中。硝酸盐氮是工业废水中的主要污染物之一。基于UV法测量水体中硝酸盐氮浓度的标准方法是分别测量水样在220nm和275nm处的吸光度,然后用275 nm处的吸光度对220 nm处的吸光度进行校正,进而绘制出校正后的吸光度与硝酸盐氮浓度的标准曲线。然而,当硝酸盐氮浓度升高时,标准法所采用的朗伯比尔定律的线性关系以及不同物质吸光度叠加的线性不能很好地满足,在实际的实验测试中也发现,很难建立硝酸盐氮在220 nm处的吸收模型。为了克服单波长或双波长方法的缺陷,将硝酸盐氮吸收峰范围的各个波长的吸光特性引入到模型的建立之中。同时,为了降低模型的复杂度,在建立模型之前先对吸光度数据进行主成分分析,将输入数据的维度数从107压缩到4,然后对压缩后的数据使用局部加权线性回归法建模,该吸收模型对于训练样本和测试样本都有较好的预测结果,且能够适应高浓度时吸光度与浓度的非线性关系,测量上限可达几百mg·L-1。另外,此方法的原理和流程也适用于其他水质参数吸收模型的建立。     

AA3型连续流动分析仪测定天然泉水中的亚硝酸盐氮

建立应用AA3连续流动分析仪测定天然泉水中亚硝酸盐氮的方法。在0-5.00mg·L^-1线性区间内该方法线性关系好,较高的精密度和准确度,检出限低。与GB／T8538-2008饮用天然矿泉水检验方法中亚硝酸盐氮分光光度法相比,该方法具有自动进样、分析速率快、试剂耗量低等优点,可应用于大批量天然泉水分析.     

The impact of ozone on the (15)n incorporation and nitrogen assimilation of wheat and maize

Abstract Young wheat (C3) and maize (C4) plants were exposed to near-ambient concentrations of ozone in open-top chambers in order to investigate the possible effects of ozone on nitrogen metabolism. Nitrogen was supplied to the plants by adding (15)N-labelled tracer substances via the soil substrate. Enzyme activities (NADH nitrate reductase, nitrite reductase, glutamine synthetase and NADH glutamate dehydrogenase) and the incorporation of (15)N were determined. The findings show that nitrogen metabolism was affected by O(3), however, there were distinct differences between the two species. In plants treated with O(3), NADH nitrate reductase activity in maize leaves was reduced, while NR activity in wheat leaves only slightly declined. Only minor changes were observed with respect to the activities of nitrite reductase, glutamine synthetase and NADH glutamate dehydrogenase. Feeding experiments using (15)NO(3) (-) showed that the incorporation of nitrate nitrogen in wheat plants exposed to ozone remains virtually unchanged, whereas in maize plants reduced incorporation rates were observed for nitrate nitrogen. The incorporation of ammonium nitrogen was distinctly increased in wheat and maize by the impact of ozone. When investigating pigment contents, reduced levels of chlorophyll a and b and carotenoids were observed, whereas the pigment content of wheat leaves remained unchanged. These results indicate that young maize plants are more susceptible than wheat plants to short-term ozone exposure.     

Determination of (15)N in (15)N-enriched nitrite and nitrate in aqueous samples by reaction continuous flow quadrupole mass spectrometry

The (15)N tracer method is the most suitable method for studying complex N transformation processes in microbiology and biochemistry. It entails the constant determination of the (15)N abundance of the inorganic nitrogen (N) compounds nitrite and nitrate. However, (15)N analytical methods are time-consuming, difficult to automate, and require at least 10 μg of N per determination. An additional obstacle in the case of nitrite is that it usually only occurs in very small amounts (ppb) dwarfed by much larger quantities of nitrate (ppm). More useful is an approach in which the N compound is selectively converted into a gaseous form suitable for direct measurement by mass spectrometry. By using this 'reaction continuous-flow mass spectrometry' (R/CFMS) we developed methods for the (15)N determination of nitrite and nitrate from tracer experiment samples, i.e. artificially enriched in (15)N. Because both methods are based on the same principle, one continuous flow setup connected directly to a quadrupole mass spectrometer for all determinations was used. Nitrite and nitrate are reduced to NO by iodide and titanium(III) chloride, respectively. The technique developed ensures a precision of relative standard deviation /=1 at.% are to be measured for nitrite and nitrate, respectively. Copyright 1999 John Wiley & Sons, Ltd.     

Rapid, Sensitive and Highly Selective (15)N Analysis of (15)N Enriched Nitrite in Water Samples and Soil Extracts by Nitric Oxide Production and CF-QMS Measurement

Abstract Nitrite is a very important intermediate in many microbiological N transformations in soils and water. The stable isotope (15)N is often used to investigate these processes. The determination of (15)N in low concentrations of nitrite in the presence of large concentrations of nitrate is very difficult. Methods used so far for the isotope analysis of nitrite are unsatisfactory, because the nitrite must be calculated as the difference between nitrate plus nitrite and nitrate alone. More useful are mehods by which the nitrite is selectively converted into a chemical form that is suitable for (15)N analysis and that is free from interference from other N species, particularly nitrate. Using this principle in the present study we developed a method where the nitrite is reduced to nitric oxide by iodide in acid medium. This reaction is fast and quantitative, and the (15)N abundance of NO can be precisely measured by continuous flow mass spectrometry. This method is used for samples from tracer experiments with artificially enriched nitrogen 15. Therefore, the use of simple quadrupole mass spectrometers directly linked to the reaction unit is possible with sufficient precision (Reaction-Continuous Flow Quadrupole Mass Spektrometry-RCFQMS). Using the technique developed sample volumes up to 10ml containing at least 1.0 μg nitrite-N (0, 1 μg/ml) with a (15)N abundance of ? 0.42 at.% gave a precision of RSD ? ± 3%.     

Application of capillary electrophoresis in anion binding studies: Complexation and separation of nitrate and nitrite by an azacryptand

Capillary electrophoresis (CE) was employed for studying the complexation of an azacryptand with nitrate and nitrite in aqueous solution. CE separation of a mixture of nitrate and nitrite with 10 mM acetate buffer (pH 3.3) showed two peaks at the retention times of 2.8 and 3.1 min for nitrate and nitrite, respectively. However, when the ligand (2 mM) was added to the running buffer, the peaks emerged in the reverse order and at shorter retention times of 2.7 and 2.5 min for nitrate and nitrite, respectively. The longer retention time for nitrate compared with nitrite indicates a stronger complex formation between the ligand and nitrate, that reduces the migration speed of nitrate as compared with the less strongly bound nitrite. The (1)H NMR titrations of L with these two anions at the pH 3.3, gave the binding constants (log K), 3.75 and 4.23, for nitrite and nitrate, respectively which were in consistence with the results obtained from the CE method.     

Nitrogen diffusion through cementite layers

Massive cementite layers with a time-dependent thickness were grown on ferrite substrates by nitrocarburising in a dedicated NH₃/H₂/CO/N₂-containing gas atmosphere at 783 K, 823 K and 843 K. Nitrogen diffusion through the cementite layer into the ferrite substrate took place in conjunction with growth of the cementite layer; a significant, i.e. measurable, solubility of nitrogen in cementite was not observed. The nitrogen concentration-depth profiles in the substrate, underneath the growing cementite layer, were quantitatively determined using a calibrated microhardness measurement technique. The nitrogen concentration-depth profiles were simulated on the basis of a model using an implicit finite-difference method. The simulation yielded values for the diffusivity of nitrogen through cementite, including its activation energy.     

浆氮制备及其管内流动特性的实验研究

本文对冻结一融化法制备浆氮进行了研究,考查了真空泵抽速及冻结、融化时间对浆氮性质的影响,得到了制备含有细小固氮颗粒浆氮的方法。并研究了浆氮在内径10 mm的水平长直圆管中的流动性质。实验结果表明,当真空泵抽速大于4 L/s且冻结与融化时间分别为10 s与5 s时制备效率高且生成的固氮颗粒直径约1 mm。浆氮在水平圆管内流动时单位长度的压降略高于液相压降,且随流速和固相体积分数的增加而增加,在低速时固相体积分数对流动压降有明显影响。