Multivariate analysis of fluorescence and source identification of dissolved organic matter in Jiaozhou Bay, China

Hierarchical clustering analysis and principal component analysis (PCA) methods were used to assess the similarities and dissimilarities of the entire Excitation-emission matrix spectroscopy (EEMs) data sets of samples collected from Jiaozhou Bay, China. The results demonstrate that multivariate analysis facilitates the complex data treatment and spectral sorting processes, and also enhances the probability to reveal otherwise hidden information concerning the chemical characteristics of the dissolved organic matter (DOM). The distribution of different water samples as revealed by multivariate results has been used to track the movement of DOM material in the study area, and the interpretation is supported by the results obtained from the numerical simulation model of substance tracing technique, which show that the substance discharged by Haibo River can be distributed in Jiaozhou Bay.     

兴凯湖沉积物磁化率和色度反映的28kaBP以来区域古气候环境演化

对兴凯湖长269 cm的沉积岩心的研究结果显示:沉积物的色度和磁化率特征可以较好地反映区域气候环境变化。沉积物明度分别与红度、磁化率、黏土和有机质含量之间及磁化率与黏土之间有很好的相关性;红度高值与明度低值对应暖湿气候环境,磁化率低值反映沉积物较粗的较低湖面,对应冷干气候。28480~26160 cal.aBP,湖区处于温湿气候时期;22880~18170 cal.aBP,岩心孢粉浓度很低,流域处于末次盛冰期疏桦林草原环境;18170~12650 cal.aBP处于Bφlling/Older Dryas/Allerφd暖期。岩心深度90~78 cm段,对应于新仙女木期;11500~4570 cal.aBP,进入全新世暖期,其中8000~5000 cal.aBP,本区处于全新世大暖期(气候适宜期);4570~1470 cal.aBP气候变为凉干;1470 cal.aBP以来,流域又变为暖湿气候环境,同时,人类活动逐渐增强造成水土流失加剧。     

Fabry-Perot spectroscopy in space science

The paper describes use of Fabry-Perot (fp) systems in spectroscopic studies of astronomy and earth’s upper atmosphere. Factors influencing the resolution, luminosity and instrumental line shape offp spectrometer are discussed and the need for their optimization is emphasised, if desired luminosity gain is to be realised in practice. Use offp as imaging spectrometer, scanning spectrometer and as a narrow band filter are illustrated. Tandemfp systems are briefly dealt with.     

Measurements of tropospheric OH concentrations: A comparison of field data with model predictions

Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×10⁶ to 3.2×10⁶ cm^-3. Simultaneously we measured the concentrations of O₃, H₂O, NO, NO₂, CH₄, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O₃ and NO₂. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO _x concentrations. It is argued that additional, so far unidentified. HO _x loss reactions must be responsible for that discrepancy.     

Infrared estimates of aliphatic kerogen carbon in sedimentary rocks

An infrared routine has been developed to estimate the aliphatic portion of kerogen carbon in sedimentary rocks. The procedure does not require isolation of the organic matter and is based on a computer-assisted determination of global band areas in the region of the aliphatic carbon-hydrogen stretching vibrations around 2900cm⁻¹. From these integrated absorptions the amount of aliphatic carbon C_al (mg of aliphatic carbon per gram of solvent-extracted rock) is calculated by means of a calibration with model rocks. Carbonate overtones which interfere in the case of limestones are eliminated by comparison to a CaCO₃ standard.The method has been applied to rocks containing kerogens of different types and maturities at TOC levels of 0.5 to 12%. The aliphatic carbon concentrations range from 0.5 to 60mg·g⁻¹ and correlate reasonably well with the residual genetic potentials of the rocks as measured by S₂ values from Rock-Eval pyrolysis. The ratio S₂/C_al is found to decrease with burial depth reflecting a maturity enhanced conversion of aliphatic carbon to fixed aromatic carbon under Rock-Eval conditions.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.     

<Superscript>57</Superscript>Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. ⁵⁷Fe Mössbauer spectra are consistent with the assumption that high-spin Fe³⁺ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with ⁵⁷Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe²⁺. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe³⁺ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe³⁺ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe²⁺. However, it cannot be excluded that Fe²⁺ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H₂O molecule.     

Analysis of Physical and Chemical Parameters for Discrimination of Water Origin in a Hydroelectric Reservoir

Seventeen physical and chemical parameters were obtained from a hydroelectric reservoir located in a tropical region in the south of Brazil. Multivariate Principal Component Analysis (PCA) and Hierarchical Group Analysis (HGA) were used to identify the parameters discriminating the origin of water from the Tibagi and the Primeiro de Maio River, after it has passed the mixing region. The study was conducted during the dry and rainy seasons in July 2002 and February 2003 at three depths and three sampling sites located 0, 5, and 10 km away from the mixing region. The statistical methods showed to be appropriate for identifying the contribution of each tributary in the water mixing site of a complex water system. The most important discriminating parameter was the absorbance relation A(253 nm)/A(203 nm), followed by the concentrations of Fe(III), Mn(III), and Ni(II). An anthropogenic interference was found in the reservoir due to high Ni(II) and orthophosphate concentrations caused by a nearby town sewage discharge. The interference was more important during the dry periods due to the lower dispersion of the pollutants. Urgent initiatives should be taken from the state government to build treatment stations for the wastewater of the small cities around the Capivara hydroelectric reservoir to prevent the drinking water quality from deteriorating.     

Use of high spectral resolution remote sensing to determine leaf palatability of eucalypt trees for folivorous marsupials

In this study we assess the feasibility of remotely measuring canopy biochemistry, and thus the potential for conducting large-scale mapping of habitat quality. A number of studies have found nutrient composition of eucalypt foliage to be a major determinant of the distribution of folivorous marsupials. More recently it has been demonstrated that a specific group of secondary plant chemicals, the diformylphloroglucinols (DFPs), are the most important feeding deterrents, and are thus vital determinants of habitat quality. We report on the use of laboratory spectroscopy to attempt to identify one such DFP, sideroxylonal-A, in the foliage of Eucalyptus melliodora, one of the few eucalypt species browsed by folivorous marsupials. Reflectance spectra were obtained for freeze-dried, ground leaves using near infrared spectroscopy (NIRS) and for both oven-dried and fresh whole leaves using a laboratory-based (FieldSpec) spectroradiometer. Modified partial least squares (MPLS) regression was used to develop calibration equations for sideroxylonal-A concentration based on the reflectance spectra transformed as both the first and second difference of absorbance (Log 1/R). The predictive ability of the calibration equations was assessed using the standard error of calibration statistic (SECV). Coefficients of determination (r²) were highest for the ground leaf spectra (0.98), followed by the fresh leaf and dry leaf spectra (0.94 and 0.87, respectively). When applied to independent validation sub-sets, sideroxylonal-A was most accurately predicted from the ground leaf spectra (r² = 0.94), followed by the dry leaf and fresh leaf spectra (0.72 and 0.53, respectively). Two spectral regions, centred on 674 nm and 1394 nm, were found to be highly correlated with sideroxylonal-A concentration for each of the three spectral data sets studied. Results from this study suggest that calibration equations derived from modified partial least squares regression may be used to predict sideroxylonal-A concentration, and hence leaf palatability, of Eucalyptus melliodora trees, thereby indicating that the remote estimation of habitat quality of eucalypt forests for marsupial folivores is feasible.     

Location and quantitative analysis of OH in coesite

 The incorporation of hydrogen (deuterium) into the coesite structure was investigated at pressures from 3.1 to 7.5 GPa and temperatures of 700, 800, and 1100 °C. Hydrogen could only be incorporated into the coesite structure at pressures greater 5.0 GPa and 1100 °C . No correlation between the concentration of trace elements such as Al and B and the hydrogen content was observed based on ion probe analysis (1335 ± 16 H ppm and 17 ± 1 Al ppm at 7.5 GPa, 1100 °C). The FTIR spectra show three relatively intense bands at 3575, 3516, and 3459 cm⁻¹ (ν₁ to ν₃, respectively) and two very weak bands at 3296 and 3210 cm⁻¹ (ν₄ and ν₅, respectively). The band at 3516 cm⁻¹ is strongly asymmetric and can be resolved into two bands, 3528 (ν_2a) and 3508 (ν_2b) cm⁻¹, with nearly identical areas. Polarized infrared absorption spectra of coesite single-crystal slabs, cut parallel to (0 1 0) and (1 0 0), were collected to locate the OH dipoles in the structure and to calibrate the IR spectroscopy for quantitative analysis of OH in coesite (ɛ _{i ,tot}=190 000 ± 30 000 l mol⁻¹ _H2O cm⁻²). The polarized spectra revealed a strong pleochroism of the OH bands. High-pressure FTIR spectra at pressures up to 8 GPa were performed in a diamond-anvil cell to gain further insight into incorporation mechanism of OH in coesite. The peak positions of the ν₁, ν₂, and ν₃ bands decrease linearly with pressure. The mode Grüneisen parameters for ν₁, ν₂, and ν₃ are −0.074, −0.144 and −0.398, respectively. There is a linear increase of the pressure derivatives with band position which follows the trend proposed by Hofmeister et al. (1999). The full widths at half maximum (FWHM) of the ν₁, ν₂, and ν₃ bands increase from 35, 21, and 28 cm⁻¹ in the spectra at ambient conditions to 71, 68, and 105 in the 8 GPa spectra, respectively. On the basis of these results, a model for the incorporation of hydrogen in coesite was developed: the OH defects are introduced into the structure by the substitution Si^4+(Si2)+4O²⁻= ^[4]□^(Si2) + 4OH⁻, which gives rise to four vibrations, ν₁, ν_2a, ν_2b, and ν₃. Because the OH(D)-bearing samples do contain traces of Al and B, the bands ν₄ and ν₅ may be coupled to Al and/or B substitution. Received: 19 December 2000 / Accepted: 23 April 2001