Raman spectroscopic analysis of cyanobacterial colonization of hydromagnesite, a putative martian extremophile

Raman spectra of an extremophile cyanobacterial colony in hydromagnesite from Lake Salda in Turkey have revealed a biogeological modification which is manifest as aragonite in the stratum associated with the colony. The presence of key spectral biomarkers of organic protectant molecules such as β-carotene and scytonemin indicate that the survival strategy of the cyanobacteria is significantly one of UV-radiation protection. The terrestrial location of this extremophile is worthy of consideration further because of its possible putative link with the “White Rock” formations in Sabaea Terra and Juventae Chasma on Mars.     

RESOLUTION OF MULTICOMPONENT FLUORESCENT MIXTURES BY ANALYSIS OF THE EXCITATION-EMISSION-FREQUENCY ARRAY

Fluorescence lifetime provides a third independent dimension of information for the resolution of totalluminescence spectra of multicomponent mixtures.The incorporation of this parameter into theexcitation-emission matrix(EEM)by the phase modulation technique results in a three-dimensionalexcitation-emission-frequency array (EEFA).Multicomponent analysis based on the three-dimensionalEEFA brings a qualitative change for the resolved spectra,i.e.individual spectra can be uniquely resolved,which is impossible with any two-dimensional analysis.In this paper we present a method for analyzingthe EEFA.We show mathematically that with the three-dimensional analysis of the EEFA individualspectra and lifetimes can be obtained.Our algorithm is developed in mathematical detail and isdemonstrated by its application to a two-component mixture.     

Characterization of a chalcopyrite from Brazil by Mössbauer spectroscopy and other physicochemical techniques

We studied a chalcopyrite from a Cu ore deposit in Rio Grande do Sul, Brazil, by Mössbauer spectroscopy at room temperature and 110 K. Supporting methods to check for sample purity and to characterize further sample properties were slow-scanning X-ray powder diffraction and optical and microprobe analyses of polished sections of selected grains. Chemical analyses obtained using a scanning electron microscope equipped with an energy-dispersive X-ray spectrometer showed the sample to consist of homogeneous and essentially stoichiometric chalcopyrite (CuFeS₂). Mössbauer spectra taken at both the above temperatures consist of asymmetric magnetically ordered patterns with unequal intensities of the line pairs 1–6 and 2–5, pointing to the existence of non-equivalent or multiple Fe sites. Least-squares fittings evidenced that the resonance intensity ratio of subspectrum with lower quadrupole shift (indicative of a more symmetric environment) to that with higher shift is 69:31, at room temperature, and 68:32, at 110 K. Rietveld refinement of the XRD data indicates the existence of tetragonal [a = 0.52855(1) and c = 1.0412(1) nm] and cubic [a ₀ = 0.5273(2) nm] modifications in a proportion of 74:26, in good agreement with the Mössbauer data. The saturation magnetization of the sample was 32.7 J/(T kg), confirming the oxidation state of Fe as trivalent and pointing to little to no spin canting.     

北京地区Landsat 8 OLI高空间分辨率气溶胶光学厚度反演

卫星气溶胶光学厚度(AOD)反演中,传统暗目标方法在反射率较低的水体、浓密植被覆盖区域取得了较好效果,在反射率较高且结构复杂的高反射地表上空目前多采用深蓝算法,但存在空间分辨率较低,对细节分布描述性较差等问题。为解决这一问题,本文首先以5年(2008年—2012年)长时间序列MODIS地表反射率产品为基础,采用最小值合成法建立500 m分辨率逐月地表反射率产品数据集,然后利用地物波谱库中典型地物波谱数据,分析建立MODIS与Landsat 8 OLI传感器蓝光波段反射率转换模型,最后北京地区AERONET地基观测数据确定了气溶胶光学物理参数,并反演获取了北京地区上空500 m分辨率的AOD分布。为验证反演算法的精度,分别将反演结果同AERONET及MODIS/Terra气溶胶产品(MOD04)进行交叉对比,同时利用相关系数R,均方根误差RMSE,平均绝对误差MAE以及MODIS AOD产品预期误差EE共4个指标进行衡量。结果表明:算法反演获取的AOD与AERONET观测值具有较高的一致性,各指标分别为R=0.963,RMSE=0.156,MAE=0.097,EE=85.3%,稍优于MOD04产品(R=0.962,RMSE=0.158,MAE=0.101,EE=75.8%),并且有效的对比点数也高于MOD04。通过与地基观测相比,卫星遥感获取的高分辨率城市地区AOD精度可作为定量评估城市空气质量的有效依据。     

水面菲涅尔反射对~761 nm叶绿素荧光估算的影响

叶绿素荧光是光合作用的有效探针,可用于海洋浮游植物的监测与定量评估。太阳诱导叶绿素荧光覆盖可见光—近红外650—800 nm,在～685 nm与～740 nm表现出两个形态不同的荧光峰特征。基于～685 nm荧光峰的叶绿素浓度反演算法较为成熟,但在高悬浮物和高叶绿素浓度的水体中,算法的有效性不足。基于叶绿素荧光在氧气吸收谱段(O2-A)的填充作用,水体遥感反射率光谱～761 nm峰值中包含有太阳诱导叶绿素荧光信号,能用于水体叶绿素浓度的估算,但该反射峰形态特征还取决于传感器的光谱分辨率。本研究基于不同光谱分辨率的大气吸收谱线特征,模拟了水体遥感反射率光谱(750—775 nm)上太阳诱导叶绿素荧光的信号响应特征;分析了利用遥感反射率(～761 nm)计算叶绿素荧光的原理,阐明了不同光谱分辨率条件下水体叶绿素荧光信号在反射光谱上的形态变化规律。采用水面以上测量法获取的离水光谱辐亮度,包含了水面的菲涅尔反射信号,由于真实的菲涅尔系数难以准确测量,这给基于～761 nm处遥感反射率峰值的荧光信号估算带来不确定性影响。研究表明,假定菲涅尔系数为0时,虽然～761 nm叶绿素荧光信号与其浓度具有较好的线性统计关系,但却带来较大的不确定性;这种不确定的影响,在低浓度叶绿素水体中表现明显,在高浓度叶绿素水体中,影响相对较小;准确估算菲涅尔系数,有助于减少这种不确定性影响。对基于遥感反射率～761 nm叶绿素荧光信号的深入探讨,将能推动未来水体叶绿素荧光的识别与利用。     

Calibration of Infrared Absorption Coefficients for Structural Hydroxyl in Garnet by a Combined Study of Isotope Ratio Spectrometry and Vibrational Spectroscopy

An accurate determination of water content in garnet is critical to quantify the transport of water to the deep mantle by the subducted oceanic crust beyond the breakdown of hydrous phases. Fourier transform infrared spectroscopy (FTIR) is the most widely used approach to determine the species and contents of water in garnet. Accurate quantification of OH in garnet requires independent calibration using an external method, as OH absorbance is mineral and composition specific. To obtain the infrared absorption coefficients of structural hydroxyl in garnet, a combined study of spectrometric analyses by FTIR and a method combining a thermal conversion elemental analyser with isotope ratio mass spectrometry (TC/EA-MS) was carried out for fourteen gem-quality natural garnet crystals with variable compositions. The obtained molar absorption coefficients were 9322 ± 338 and 240 ± 26 l mol⁻¹ cm⁻² for grossular- and spessartine-rich garnet and pyrope-almandine garnet, respectively. These results are within the range of previous studies. A new molar absorption coefficient of 689 ± 177 l mol⁻¹ cm⁻² was obtained for pyrope-spessartine garnet. The large variation in the absorption coefficient indicates it is controlled by both garnet composition and OH-absorption bands. The obtained absorption coefficients are only appropriate for certain types of eclogitic garnet, and more studies should be carried out on eclogitic garnets.     

基于可见—近红外反射光谱的典型农田重金属污染风险分类研究

对于人为因素或自然因素造成的农田土壤重金属元素污染,需要进行大面积的土壤环境质量调查和分类管控,然而传统的采样测试方法存在工作量大、代价高等问题。可见—近红外（Vis-NIR）反射光谱是一种快速低成本获取土壤理化信息的手段。为研究Vis-NIR反射光谱预测模型划分土壤重金属污染风险类别的能力,文章以典型人为污染地区（浙江温岭）和典型地质高背景地区（广西横县）的390份农田土壤为样本,测定8种重金属元素（As、Cd、Cr、Cu、Hg、Ni、Pb和Zn）的含量和pH值,并测定土壤Vis-NIR光谱。使用偏最小二乘（PLS）和支持向量机（SVM）算法建立回归模型,对土壤重金属含量和pH值进行预测,并基于预测值进行土壤重金属污染风险分类。结果显示,温岭土壤主要污染元素Cd和Cu的光谱模型回归预测偏差（RPD）分别为1.23和1.19,预测机制与有机质有关。横县土壤主要污染元素As和Cd的RPD分别为1.98和1.93,预测机制与铁氧化物和粘土矿物有关。地质高背景土壤重金属与铁氧化物的正相关性普遍较强,使得光谱模型对重金属含量预测准确度较高。温岭和横县土壤pH值的光谱模型RPD分别为1.76和1.68。土壤重金属污染风险光谱分类的总体 准确度分别为75.0%~100%（温岭）和80.0%~100％（横县）。将Vis-NIR光谱与遥感技术相结合,对农田土壤重金属污染风险进行快速分类总体是可行的。     

Raman Micro-Spectroscopic Study of Sulfate Ion in the System Na2SO4 – H2O

This work aims to quantify sulfate ion concentrations in the system Na₂SO₄-H₂O using Raman micro-spectroscopy.Raman spectra of sodium sulfate solutions with known concentrations were collected at ambient temperature（293 K） and in the 500 cm^₁-4000 cm^-1 spectral region.The results indicate that the intensity of the SO₄^2- band increases with increasing concentrations of sulfate ion.A linear correlation was found between the concentration of SO₄^2-（c） and parameter I₁,which represents the ratio of the area of the SO₄^2- band to that of the O-H stretching band of water（A_s/A_w）:I₁=-0.00102+0.01538 c.Furthermore,we deconvoluted the O-H stretching band of water(2800 cm^-1-3800 cm^-1) at 3232 and 3430 cm^-1 into two sub-Gaussian bands,and then defined Raman intensity of the two sub-bands as A_Bi(3232 cm^-1) and A_B2(3430 cm^-1),defined the full width of half maximum（FWHM） of the two sub-bands as W_B1(3232 cm^-1) and W_B2(3430 cm^-1).A linear correlation between the concentration of SO₄^2-（c） and parameter I₂,which represents the ratio of Raman intensity of SO₄^2-（A_s）(in 981 cm^-1) to(A_B1+A_B2),was also established:I₂=-0.0111+0.3653 c.However,no correlations were found between concentration of SO₄^2-（c） and FWHM ratios,which includes the ratio of FWHM of SO₄^2-（W_s） to W_B1 W_B2 and W_B1+B2(the sum of W_B1 and W_B2),suggesting that FWHM is not suitable for quantitative studies of sulfate solutions with Raman spectroscopy.A comparison of Raman spectroscopic studies of mixed Na₂SO₄ and NaCI solutions with a constant SO₄^2- concentration and variable CI^- concentrations suggest that the I\ parameter is affected by CI^-,whereas the I₂ parameter was not.Therefore,even if the solution is not purely Na₂SO₄-H₂O,SO₄^2- concentrations can still be calculated from the Raman spectra if the H₂O band is deconvoluted into two sub-bands,making this method potentially applicable to analysis of natural fluid inclusions.     

冠层反射光谱对植被理化参数的全局敏感性分析

植被理化参数与许多有关植物物质能量交换的生态过程密切相关,定量分析植被反射光谱对理化参数的敏感性是遥感反演理化参数含量的前提。本文采用EFAST(Extended Fourier Amplitude Sensitivity Test)全局敏感性分析方法,利用PROSAIL辐射传输模型分析了冠层疏密程度对叶片生化组分含量、冠层结构以及土壤背景等多种参数敏感性的影响,并对植被理化参数反演所需先验知识的精度问题进行了初步探讨。研究表明:(1)对于较为稠密的冠层,可见光波段的冠层反射率主要受叶绿素含量的影响,近红外和中红外波段的冠层反射率主要受干物质量和含水量的影响;(2)对于稀疏的冠层,LAI是影响400—2500 nm波段范围内冠层反射率的最重要参数,土壤湿度次之,叶片生化参数对冠层反射率的敏感性较低;(3)在已知稀疏冠层LAI的情况下进一步确定土壤的干湿状态,可显著提高冠层反射率对叶绿素含量的敏感度,有助于稀疏冠层叶绿素含量的反演。