EVALUATION OF THE EFFECT OF WAVELENGTH POSITIONING ERRORS ON KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This work evaluates the effect of wavelength positioning errors in spectral scans on analytical results when the Kalman filtering technique is used for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a positioning accuracy of 0.1 pm is required in order to obtain accurate and precise estimates for analyte concentrations. The positioning error in sample scans is more crucial than that in model scans. The relative bias in measured analyte concentration originating from a positioning error in a sample scan increases linearly with an increase in the magnitude of the error and the peak distance of the overlapping lines, but is inversely proportional to the signal-to-background ratio. By the use of an optimization procedure for the positions of scans with the innovations number as the criterion, the wavelength positioning error can be reduced and, correspondingly, the accuracy and precision of analytical results improved.

IMPROVEMENT OF SELECTIVITY WITH NUMERICAL DERIVATIVE TECHNIQUES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

One of the most attractive features of derivative spectrometry is its higher resolving power. In the present power, numerical derivative techniques are evaluated from the viewpoint of increase in selectivity, the latter being expressed in terms of the interferent equivalent concentration (IEC). Typical spectral interferences are covered, including flat background, sloped background, simple curved background and various types of line overlap with different overlapping degrees, which were defined as the ratio of the net interfering signal at the analysis wavelength to the peak signal of the interfering line. the IECs in the derivative spectra are decreased by one to two order of magnitudes compared to those in the original spectra, and in the most cases, assume values below the conventional detection limits. The overlapping degree is the dominant factor that determines whether an analysis line can be resolved from an interfering line with the derivative techniques. Generally, the second derivative technique is effective only for line overlap with an overlapping degree of less than 0.8. The effects of other factors such as line shape, data smoothing, step size and the intensity ratio of analyte to interferent on the performance of the derivative techniques are also discussed. All results are illustrated with practical examples.

SEARCH FOR THE BASIC REGULARITIES OF THE TRANSITION EMISSION OF EUROPIUM(II) ION IN COMPLEX FLUORIDES USING PATTERN-RECOGNITION

The relationship between structures of complex fluorides and spectral structure of Eu(II) ion in complex fluorides (AB(m)F(n)) is investigated by means of pattern recognition methods, such as KNN, ALKNN, BAYES, LLM, SIMCA and PCA. A learning set consisting of 32 f-f transition emission host compounds and 31 d-f transition emission host compounds and a test set consisting of 27 host compounds were characterized by 12 crystal structural parameters. These parameters, i.e. features, were reduced from 12 to 6 by multiple criteria for the classification of these host compounds as f-f transition emission or d-f transition emission. A recognition rate from 79.4 to 96.8% and prediction capabilities from 85.2 to 92.6% were obtained. According to the above results, the spectral structures of Eu(II) ion in seven unknown host lattices were predicted.

MEASUREMENT AND CALCULATION OF SPONTANEOUS EMISSION BRANCHING RATIOS, RELATIVE OSCILLATOR-STRENGTHS, TRANSITION-PROBABILITIES AND LEVEL LIFETIMES FOR ATOMIC URANIUM

We propose a laser induced sensitized fluorescence spectrometry for measuring the spontaneous emission branching ratios o?the transitions from the ten levels 5f36d7s7p-7M7, 5f36d7s7p-7L6, 5f37s27p-5K6, 5f26d27s2 - 5L7, 5f46d7s - 7L6, (17,070cm-1)-5L6, 5f26d27s2-5K6, 6d7s7p-7L5, 5f36d7s7p-7K5 and 5f26d27s2-5I5 to the ground state of atomic uranium (UI) for the first time. Their relative oscillator strengths have been measured by means of hollow cathode discharge (HCD) emission spectrometry. The radiative...

CRITERION ON F-]F TRANSITION EMISSION OF EUROPIUM(II) AND ITS APPLICATION IN COMPLEX FLUORIDES

The criterion on 4f~7(~6P_J)→4f~7 (~8S_(7/2))(i. e. f→f)transition emission of Eu~(2+) ions was established based on chemical band properties and crystal field effects. By means of the criterion, we have predioted, designed and synthesized 40 Eu~(2+)-doped complex fluorides. The sharp emissions of f→f transition of Eu~(2+) ions were observed in these doped compounds. The condition for applying this criterion is briefly discussed.

MEASUREMENT OF SPONTANEOUS EMISSION BRANCHING RATIOS IN MO(I) TRANSITIONS BY LASER-INDUCED SENSITIZED FLUORESCENCE

I. TNTRODUCTIONThe emission spectroscopic method is usually used to measure spontaneous emission branching ratios. As emission spectra cannot be detected in atomic beams, the laser-induced fluorescence or ion detection method is often used. When the fluorescence method is used to measure branching ratios, it is usually necessary to detect

THE INFLUENCE OF CRYSTAL-FIELD AND COVALENT CHARACTERISTICS ON THE ELECTRONIC-TRANSITION EMISSION OF EU-2+ ION

In most cases the luminescence of Eu~(2+) consists of a d-f broad-band emission, in some particular hosts, however, Eu~(2+) can also give out f-f narrow-line emission. There are two factors of importance here: the first is the strength of the crystal-field

Three-dimensional fluorescence characteristics of dissolved organic matter produced by Prorocentrum donghaiense Lu

Filtration and cross-flow ultrafiltration techniques were used to separate culture media of Prorocentrum donghaiense at the exponential growth, stationary and decline stages into < 0.45 mu m filtrate, 100 kDa-0.45 mu m, 10-100 kDa and 1-10 kDa retentate and < 1 kDa ultrafiltrate fractions. The fluorescence. properties of different molecular weights of dissolved organic matter (DOM) were measured by excitation-emission matrix spectra. Protein-like and humic-like fluorophores were observed in the DOM produced by P. donghaiense. The central positions of protein-like fluorophores showed a red shift with prolonged growth duration, shifting from tyrosine-like properties at the exponential growth stage to tryptophan-like properties at the stationary and decline stages. The excitation wavelengths of protein-like fluorophores exhibited some change in the exponential growth and stationary stages with increased molecular size, but showed little change in the decline stage. However, the emission wavelengths in the decline stage exhibited a blue shift. Very distinct C type and A type peaks in humic-like fluorophores were observed. With a prolonged culture time, the intensities of both of the peaks became strong and the excitation wavelengths of peak A showed a red shift, while the A:C ratios fell. More than 94% of fluorescent DOM was in the lower than 1 kDa molecular weight fraction.

Three dimensional fluorescence excitation-emission on matrix spectrum of dissolved organic substance in marine microalgaes growth process

The three-dimensional fluorescence spectrum was used to detect the changes in dissolved organic substances from the cultured Skeletonema costatum, Alexandrium tamarense, Alexandrium mimutum, Scrippsiella trochodea, Prorocentrum donghaiense and Prorocentrum micans. The result indicates that all of the microalgaes can produce FDOM in the growth courses. Diatom such as Skeletonema costatum can produce humic-like FDOM. However dinoflagellate can produce protein-like FDOM at exponential growth phase. When the algae grows into decadency phase, the intensity of humic-like and protein-like fluorescence augments rapidly, which may be due to a mass of FDOM realeased by the old or dead cell fragmentation and the degradation of bacteria by using non-FDOM. The fluorescent intensity of Alexandrium tamarense, Alexandrium mimutum, Prorocentrum donghaiense and Prorocentrum micans can reduce at anaphase of decadency phase because of the degradation of bacteria and light. The same genus of algae can produce similar FDOM, for example: Alexandrium tamarense, and Alexandrium mimutum, Prorocentrum donghaiense and Prorocentrum micans, but the positions of the fluorescence peaks are different.

Effects of forage composition and growing season on methane emission from sheep in the Inner Mongolia steppe of China

Understanding the effects of dietary composition on methane (CH4) production of sheep can help us to understand grassland degradation resulting in an increase of CH4 emission from ruminant livestock and its resulting significance affecting CH4 source/sink in the grazing ecosystem. The objective of this study was to investigate the effect of forage composition in the diet of sheep in July and August on CH4 production by sheep in the Inner Mongolia steppe. The four diet treatments were: (1) Leymus chinensis and Cleistogenes squarrosa (LC), (2) Leymus chinensis, Cleistogenes squarrosa and concentrate supplementation (LCC), (3) Artemisia frigida and Cleistogenes squarrosa (AC), and (4) Artemisia frigida, Cleistogenes squarrosa and concentrate supplementation (ACC). CH4 production was significantly lower in July than in August (31.4 and 36.2 g per sheep-unit per day, respectively). The daily average CH4 production per unit of digestive dry matter (DM), organic matter (OM) and neutral detergent fiber (NDF) increased by 10.9, 11.2 and 42.1% for the AC diet compared with the LC diet, respectively. Although concentrate supplementation in both the AC and LC diets increased total CH4 production per sheep per day, it improved sheep productivity and decreased CH4 production by 14.8, 12.5 and 14.8% per unit of DM, OM and NDF digested by the sheep, respectively. Our results suggested that in degraded grassland CH4 emission from sheep was increased and concentrate supplementation increased diet use efficiency. Sheep-grazing ecosystem seems to be a source of CH4 when the stocking rate is over 0.5 sheep-units ha(-1) during the growing season in the Inner Mongolia steppe.