Optical properties of low molecular weight and colloidal organic matter: Application of the ultrafiltration permeation model to DOM absorption and fluorescence

Cross-flow ultrafiltration (CFF) is often used to obtain separation and concentration of colloids from bulk natural water samples. Application of the ultrafiltration permeation model allows the quantitative determination of the low molecular weight material (LMW, < 1 kDa) and colloids in bulk dissolved organic matter (DOM) from measurements of time series permeate samples obtained from CFF. Detailed analysis of a Yukon River water sample shows that DOM absorption coefficient and fluorescence follow the permeation model and that the complex spectral optical properties of LMW DOM can be reconstructed from CFF data. A combination of measured and modeled data indicates that the LMW contribution to bulk DOM optical properties obtained from CFF can be grossly underestimated by the use of a low concentration factor (CF, the ratio of initial sample volume to retentate volume). Even at a relatively high CF of 19, optical properties of LMW DOM calculated from measurements of the retentate or integrated permeate would underestimate true values by 5–36%. In the Yukon River sample, LMW dissolved organic carbon represented 26% of the bulk concentration, but only 3–14% of the colored DOM was in the LMW fraction while 31–33% of bulk DOM florescence was due to LMW DOM. The contrasting optical properties of LMW and colloidal DOM support the concept that analysis of bulk DOM absorption and fluorescence properties reveals information about DOM molecular weight.     

Spectrophotometric pH measurement in estuaries using thymol blue and m-cresol purple

The conditional acid dissociation constants (pK_a′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pK_a′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln⁻¹):

The estimated accuracy of pH measurements using these calculated pK_a′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities.     

Analysis and classification of hyperspectral data for mapping land degradation: An application in southern Spain

Desertification is a severe stage of land degradation, manifested by “desert-like” conditions in dryland areas. Climatic conditions together with geomorphologic processes help to mould desert-like soil surface features in arid zones. The identification of these soil features serves as a useful input for understanding the desertification process and land degradation as a whole. In the present study, imaging spectrometer data were used to detect and map desert-like surface features. Absorption feature parameters in the spectral region between 0.4 and 2.5 μm wavelengths were analysed and correlated with soil properties, such as soil colour, soil salinity, gypsum content, etc. Soil groupings were made based on their similarities and their spectral reflectance curves were studied. Distinct differences in the reflectance curves throughout the spectrum were exhibited between groups. Although the samples belonging to the same group shared common properties, the curves still showed differences within the same group.Characteristic reflectance curves of soil surface features were derived from spectral measurements both in the field and in the laboratory, and mean reflectance values derived from image pixels representing known features. Linear unmixing and spectral angle matching techniques were applied to assess their suitability in mapping surface features for land degradation studies. The study showed that linear unmixing provided more realistic results for mapping “desert-like” surface features than the spectral angle matching technique.     

岩矿石吸收系数的算和测定方法

岩矿石吸收系数是钻孔电磁波法解决地质问题的重要的物性参数。岩矿石有无吸收系数的差异，是开展钻孔电磁波法能否奏效的前提．了解岩矿石的吸收系数可对钻孔电磁波法的透距和分辨力作出估计，并可为钻孔电磁波的反演解释提供重要的依据．本文不但给出了岩矿石吸收系数的计算方法，也给出了室内岩矿石标本吸收系数的测定方法和野外实测岩矿石吸收系数的方法。     

线翼截断方式对大气辐射计算的影响

在大气辐射传输计算方法中,有3种基本方法,即,逐线积分方法,k-分布方法和带模式方法。其中,逐线积分方法是最精确的计算大气透过率的方法,本文根据透过率计算方式的不同,将逐线积分方法分为追线积分法和追点积分法。由于逐线积分计算需要耗费大量的计算时间,在大气遥感和大气探测业务中使用时,必须减少计算成本,提高计算速度。本文在追线积分法的基础上,给出了简化的逐线积分的基本方法,在保证同样计算精度的同时,大大提高了计算速度。对在精确的和简化的逐线积分下,不同线翼截断方式(CUTOFF)对吸收系数、大气透过率和冷却率的影响进行了更详细的探讨。通过数值试验发现,对谱线线翼的截断方式是影响辐射计算精度和计算速度的重要因子。在不同压力下,用CUTOFF=2计算的吸收系数误差最大;对CUTOFF=1,在大多数取样点上误差都小于2%;对CUTOFF=3或4,对绝大多数取样点上计算的吸收系数误差都在5%以内,但所用的计算时间却明显减少。大气低层的透过率对不同的计算方法和不同的线翼截断方式不敏感;对大气高层,无论是对精确的还是简化的逐线积分方法,当CUTOFF=2时的透过率结果与其他线翼截断方式的结果差别较大。通过比较,本文给出线翼截断的优选方案。     

中国地区边界层大气气溶胶辐射吸收特性

采用粒子采样法对中国２３个地区边界层气溶胶的吸收系数作了测量,研究了其分布特征。结果表明：中国地区边界层气溶胶的吸收系数在１０＾－６－１０＾－３ｍ＾－１之间,明显呈北高南低的趋势,四川盆地和贵州有一相对较高的中心,吸收系数与粒子含量之间的相关系数为０．７４,吸收系数与粒子含量的分布一致性较好。小颗粒的吸收性能好于大颗粒。     

聚氨酯泡塑富集硫脲解脱-石墨炉原子吸收光谱法测定地质样品中金铂

泡沫塑料常用于富集常规地质样品中的铂族元素,而富集后往往用高温灰化法解脱,此法操作繁琐,温度过高易使铂配合物分解为王水难以提取的不溶性残渣,导致测试结果不稳定、效率低;单独使用20 g/L硫脲溶液解脱,测试结果的重现性差。本文对此方法进行改进,采用50%王水封闭溶解试样,氯化亚锡还原,聚氨酯泡塑富集,20 g/L硫脲-20%盐酸溶液解脱,石墨炉原子吸收光谱法测定金和铂。在盐酸-氯化亚锡体系中,吸附温度为20℃,振荡时间为30 min时,金和铂的回收率均在95%以上,金和铂的检出限分别为0.23 ng/g和0.39 ng/g,精密度(RSD,n=10)分别为1.8%～10.3%和1.3%～13.3%。经国家一级标准物质验证,测定值和标准值基本相符。该方法泡塑解脱时无需高温灰化,用王水多次提取,在100℃沸水浴中即可一次完成,样品处理快捷。与高温灰化法相比,提取温度大为降低,分析流程简单,显著提高了单次测样量,且干扰小、空白值低,可以满足除王水难溶的铂矿种外大部分地质样品快速测定的需要。     

Re-parameterization of a quasi-analytical algorithm for colored dissolved organic matter dominant inland waters

Quasi-Analytical Algorithms (QAAs) are based on radiative transfer equations and have been used to derive inherent optical properties (IOPs) from the above surface remote sensing reflectance (R_rs) in aquatic systems in which phytoplankton is the dominant optically active constituents (OACs). However, Colored Dissolved Organic Matter (CDOM) and Non Algal Particles (NAP) can also be dominant OACs in water bodies and till now a QAA has not been parametrized for these aquatic systems. In this study, we compared the performance of three widely used QAAs in two CDOM dominated aquatic systems which were unsuccessful in retrieving the spectral shape of IOPS and produced minimum errors of 350% for the total absorption coefficient (a), 39% for colored dissolved matter absorption coefficient (a_CDM) and 7566.33% for phytoplankton absorption coefficient (a_phy). We re-parameterized a QAA for CDOM dominated (hereafter QAA_CDOM) waters which was able to not only achieve the spectral shape of the OACs absorption coefficients but also brought the error magnitude to a reasonable level. The average errors found for the 400–750 nm range were 30.71 and 14.51 for a, 14.89 and 8.95 for a_CDM and 25.90 and 29.76 for a_phy in Funil and Itumbiara Reservoirs, Brazil respectively. Although QAA_CDOM showed significant promise for retrieving IOPs in CDOM dominated waters, results indicated further tuning is needed in the estimation of a(λ) and a_phy(λ). Successful retrieval of the absorption coefficients by QAA_CDOM would be very useful in monitoring the spatio-temporal variability of IOPS in CDOM dominated waters.     

粉色水晶内针状包裹体的成分与分布特征研究

粉色水晶内部的针状包裹体常被认为是三组呈三方对称的金红石或蓝线石,至今未有定论。本文选取含有针状包裹体的4颗星光粉晶,利用宝石学显微镜、激光拉曼光谱仪及紫外可见分光光度计对样品进行观察与测试,以确定包裹体的分布特征及矿物种类。无损拉曼测试发现包裹体的特征振动峰949 cm-1、999 cm-1与蓝线石标准峰相匹配,可确定针状包裹体为蓝线石或与其极为相近的矿物。放大检查发现,包裹体直径约0.5μm,长度可达毫米级,近定向分布,整体上呈汇聚状,在某些位置可粗略分为三组,同组针状包裹体近似平行分布。造成六射星光的三组蓝线石立体相交,未观察到明显的三方对称关系,与水晶的结晶习性无直接关系,故认为蓝线石为先成包裹体,在水晶的生长过程中被捕获。紫外可见分光光谱仅显示粉色蓝线石的特征吸收,表明大量的粉色蓝线石包裹体对粉色水晶的粉色有一定贡献。     

不同过滤条件下黄色物质的吸收光谱演化特征分析

在实验室对青岛近岸现场水样进行处理、分析,获得了原始状态下水样和被过滤（0.22μm,0.45μm）黄色物质水样的吸收光谱数据,除进一步验证了黄色物质光谱分布模式外,还测得黄色物质光吸收随滤膜孔径的变化。30个现场样品在波长380nm处吸收系数统计平均值^—Ay（380）分析表明,当使用0.45μm过滤器对水样进行处理,所获得的^—Ay（380）值要比未经过处理的现场水样所测得的^—Ay（380）值高约2.1％;而用0.22μm过滤器对现场水样进行处理,所获得的^—Ay（380）值要比未经过处理的现场样品所测得的^—Ay（380）值高约12．6％,要比用0．45μm过滤器处理的现场样品所测得的^—Ay（380）值高约10.3％,这些数据的获得为现有已获黄色物质数据的“归一化”和统一评判以及未来黄色物质测量数据的准确性判断与比较提供了参考。