水质监测中激光诱导荧光遥测技术的应用

激光诱导荧光(LIF)遥测是针对大面积水域富营养化状况进行原位、实时、快速测量的一种先进的监测技术。利用自行研制的水体污染LIF遥测系统对太湖水域进行了一次较为全面的测量,以测得的溶解有机物(DOM)荧光因子、瑞利散射因子和叶绿素a荧光因子分别代表各测量点的DOM浓度、浊度和叶绿素a浓度。同时以Skalar三维荧光成像仪测量各点DOM浓度,多参数水质分析仪测量浊度和叶绿素a浓度。对比分析了LIF遥测系统测量DOM荧光因子、瑞利散射因子和叶绿素a荧光因子与DOM浓度、浊度和叶绿素a浓度关系。结果表明LIF系统测得的DOM因子与三维荧光成像仪测量的DOM浓度值一致性较好(R=0.88733),而瑞利散射因子和叶绿素a荧光因子与多参数水质测量仪测得浊度值和叶绿素a浓度值线性相关性较差,相关系数分别为-0.39185和0.4552。对上述差异产生的可能原因进行了讨论,并阐述了LIF遥测技术在水质监测中的应用前景和潜在的应用限制。     

铅玻璃充填碧玺初探

利用常规宝石学测试、X射线荧光光谱仪（XRF）、激光诱导离解光谱仪（LIBS）、电子探针（EPMA）对近来在珠宝市场上的铅玻璃充填碧玺样品进行测试与分析,旨在探讨其鉴定特征。结果表明,该铅玻璃充填样品的充填特征不明显,与传统的有机物充填处理方法不同;X射线荧光光谱和激光诱导离解光谱的测试结果显示,该铅玻璃充填碧玺样品具有明显的Pb峰。铅玻璃充填碧玺样品中充填物的电子探针二次电子像及背散射电子像特征,可作为碧玺样品是否经过了铅玻璃充填的诊断性依据,其充填物的化学成分主要为Si和Pb,呈不规则斑块状分布于裂隙中。     

激光荧光显微探针:方法及应用

近年来研究沉积有机物的激光诱导荧光特笥和发展基于激光的荧光显微探针技术日益受到人们的重视。采用ＦＡＭＭ－９８激光荧光显微探针研究了烃源岩显微组分。研究表明,激光荧光显微探针的微束特性使 乎可以对任何显微镜下呆辨认的有机物质颗粒进行微区分析。在激光的诱导下,所有显微组分都会产生可检测到的荧光讯号。显微组分受激光束辐照最终时刻的荧光强度（Ｆ４００）以及最终荧光强度／初始荧光强度比值（Ｆ４００／Ｆo）是     

近岸沉积物再悬浮期间所释放溶解有机物的荧光特征

对采自厦门湾九龙江人海河口的4个沉积物样品进行了室内再悬浮模拟实验,利用荧光激发-发射矩阵光谱(EEMs)研究了再悬浮过程中从沉积物中释放出的有色溶解有机物(CDOM)的荧光特征,同时通过与相应站位沉积物间隙水和底层水的对比分析,探讨了河口近岸海域的沉积物再悬浮作用作为水体中溶解有机物来源之一的可能性.结果表明,对给定站位,CDOM相对荧光强度和溶解有机碳(DOC)含量分布变化非常一致,均为间隙水最高,再悬浮次之,底层水最低;站位之间,底层水和再悬浮水样中CDOM相对荧光强度随盐度的降低而增加,从海端向河端增加的趋势明显.EEMs分析表明,各样品中均存在类腐殖质荧光与类蛋白质荧光团,且模拟实验也表明再悬浮作用可释放类腐殖质与类蛋白质荧光物质到底层水中,表明底质再悬浮将是近岸水体中CDOM的一个重要来源.与相应的底层水相比,间隙水的荧光峰(如峰A/C)的位置发生红移.再悬浮样品中EEMs的荧光团同时表现出相应底层水和间隙水的特征,但是荧光峰(峰A和峰C)的最大激发和发射波长更接近底层水中相应荧光团,与间隙水相比,则发生谱峰位置的蓝移.近海端样品中荧光峰M明显,随着盐度的降低,底层水和再悬浮水样的γ(M/C)值逐渐降低,且海源的峰M由海端向河端逐渐消失,表明峰M属于海洋自生来源.本研究区域DOM的荧光指数在1.61～1.93之间,表明近海端样品DOM主要为生物来源,而近河端样品DOM主要为陆源输入,或者为陆源与生物活动共同作用的结果.     

用三维荧光谱图分析原水输送过程中藻类和有机物的变化

采用新型分析技术三维荧光谱图方法对深圳东江水源工程水体中藻类进行了荧光分析。实验结果表明,水体中有较丰富的藻类,其中蓝藻、绿藻呈优势藻种,实验期间沿程水体叶绿素a浓度在1.71~16.43μg/L之间,藻密度在72.92万~1 375万个/L之间。三维荧光方法能较好表征水体中生长藻类种类和数量,三维荧光强度F(A.U)与叶绿素a浓度Chla(μg/L)、藻密度N(104个/L)呈较好的线性关系。三维荧光方法能较好的鉴别水体中可溶性有机物腐殖酸和蛋白质,并表征其含量多少。     

骆驼山煤矿不同含水层水中荧光性DOM分布特征

结合骆驼山煤矿不同含水层水文地质条件,通过检测分析各含水层水中天然有机质三维荧光光谱、总有机碳TOC和无机阴离子,研究了荧光性溶解有机物(Dissolved Organic Matter,DOM)的分布特征,结果表明:TOC和有机物在254 mm波长紫外光下的吸光度UV₂₅₄整体上随着含水层层位加深而减少,奥灰水中TOC和UV₂₅₄比其他水体分别低2~3.3倍和2.4~4.7倍;有机物芳香度也逐渐降低,紫外吸光度SUVA值在地表水、第四系水、砂岩水和奥灰水中分别为3.28、2.27、2.24和1.96。地表水和第四系水的三维荧光光谱(3DEEM)图存在5个指纹区域,随着地层层位的加深,水中有机物总体上呈递减趋势,最深层的奥灰水中没有酪氨酸、疏水性有机酸和海洋性腐植酸,而色氨酸的荧光强度比其他水体都高,表明地下水中有机物会反应生成色氨酸类有机物。奥灰水中TOC随着地下水流向逐渐减少(从0.27 mg/L减少至0.22 mg/L);有机物反应生成色氨酸,导致色氨酸FI随着水流而逐渐增加;根据3DEEM光谱图,骆驼山煤矿区奥灰水中有机物比较稳定,能够明显区分出其作为突水水源的特征离子。      

连续流同位素质谱测定水中溶解无机碳含量和碳同位素组成的方法研究

用连续流同位素质谱对水样中溶解无机碳含量和碳同位素组成的测量方法进行了研究,使用德国Finnigan公司DeltaPlusXP同位素质谱仪和GasBenchⅡ在线制样装置对实验室制备的四个实验室标准进行了反应流程、平衡时间、信号强度、数据精度、标准稳定性等检测,结果显示平衡时间大于4h检测信号达到稳定,同时发现44CO2信号强度和水样中溶解无机碳(DIC)浓度具有很好的相关性,因此可以利用信号强度来计算原样品中的DIC浓度。在四个实验室标准中,由NaHCO3配置的标准具有非常好的稳定性和精度,可以作为测试的工作标准。本方法测量水样中溶解无机碳的δ13C分析精度为0.1‰。本方法可以广泛应用于自然界各种水体中溶解无机碳(DIC)含量及其稳定碳同位素组成的分析。     

琥珀的拉曼光谱及荧光测量研究

本文利用激光拉曼光谱研究了琥珀的化学组成,表明拉曼光谱研究琥珀的有效方法。利用MPV-3显微光度计作荧光测量表明荧光测量是可判别琥珀的真伪及评价琥珀质量的好坏的。     

应用激光扫描技术进行岩体结构面的半自动统计研究

以力丘河某边坡裸露岩体结构面的快速统计为例,提出了利用三维激光测量方法进行岩体结构面的半自动快速统计方法。详细介绍了三维激光扫描仪和高精度GPS的联合测量方法,激光点云数据的坐标转换和边坡表面三角网重构方法。在此基础上,研究了采用三维激光点云数据和三角网数据进行岩体结构面平面方程的半自动拟合方法、岩体结构面法向量和产状的关系等。利用得到的岩体结构面产状快速绘制岩体结构面密度图、玫瑰图、极点图和赤平投影图,得到了该边坡裂隙结构面分布规律和几何信息等。和传统方法相比,该方法具有快速测量和远距离测量的优点,且减少了攀爬高陡岩坡的危险。     

X射线荧光分析中的准绝对测量方法

基体效应校正是 X射线荧光分析方法中关键的一环 ,在很大程度上决定了测量数据的准确度。本文提出了一种新的基体效应校正方法—准绝对测量方法。它兼有相对测量和绝对测量方法的特点 ,并具有较广泛的适用性     

卤水中溶解性有机质的光谱学性质和光降解行为研究

卤水中溶解性有机质(dissolved organic matter,DOM)会对盐田日晒工艺和产品质量产生不利影响,如盐田卤水的蒸发速率减缓、蒸发度减小以及提取的矿物产品带有刺鼻的气味、浓重的颜色等。因此,对具有资源开发利用价值的卤水体系中DOM结构和性质的研究可以为后续DOM的有效去除或在DOM共存体系中调控无机盐结晶工艺路线提供有效的指导意见。本文以自然界中广泛存在的两种不同类型的卤水体系,即盐湖卤水DOM(SLDOM)和油田卤水DOM(OFDOM)为研究对象,采用溶解性有机碳(dissolved organic carbon,DOC)分析、光谱学分析和平行因子分析等手段对DOM的含量、分子量分布特征、光谱学结构和光降解行为开展了研究。DOC和荧光分析表明SLDOM和OFDOM的DOC含量和生物指数(BIX)值相似;与OFDOM相比,SLDOM的腐质化指数(HIX)值和高分子量组分(HMW)比例偏高;特别吸收光谱(SUVA₂₅₄)和糖类化合物含量检测结果表明,SLDOM和OFDOM的HMW组分中含有的芳香类和糖类化合物所占比例比低分子量组分(LMW)高;三维荧光谱图分析(EEM)结果表明,SLDOM主要以腐殖质类物质为主,而OFDOM以蛋白质类组分为主。此外,DOM的荧光组分在不同分子量中的分布也存在明显差异:对于SLDOM,富里酸主要分布在HMW DOM中,而腐殖酸主要在LMW DOM中;对于OFDOM,芳香胺类蛋白组分主要分布在HMW DOM中,色氨酸和酪氨酸类蛋白组分主要分布在LMM DOM中。在光降解实验中,SLDOM和OFDOM的DOC含量随光照时间增加而逐渐减少,分别下降了29.32%和15.11%。进一步的分析表明,光照过程中两种卤水中糖类化合物均减少,小分子量的DOM优先分解。此外,在光照过程中SLDOM芳香类化合物增加,腐质化程度基本不变;OFDOM芳香类化合物减少,腐质化程度增加。EEM平行因子分析(PARAFAC)结果表明,SLDOM荧光组分在光降解过程中荧光强度增加,而OFDOM荧光强度减少。     

Use of continuous measurements of dissolved organic matter fluorescence in groundwater to characterize fast infiltration through an unstable fractured hillslope (Valabres rockfall, French Alps)

Continuous measurements of natural fluorescence of dissolved organic matter (DOM) in groundwater have been used to characterize infiltration through an unstable fractured hillslope at the event time scale. Within the gneissic Valabres rockfall area in the southern French Alps, two sites, in the unstable massif and in the collapse area, were continuously monitored for electrical conductivity and for DOM natural fluorescence using a field fluorometer, and analyzed weekly for hydrochemical data. Two main results were found. From a methodological point of view, DOM natural fluorescence was a relevant tracer of fast infiltration in fissured media, knowing that continuous measurements improved the study of infiltration processes at the event time scale. From a hydrogeological point of view, the unstable fractured massif showed delayed dilution phenomena and the collapse areas showed fast and slow infiltration by piston-type flows via more or less open fractures. Consequently, from this conceptual model one may suppose that, unlike the collapse zones, the fractured hillslope threatening the valley is not submitted to strong pore-water pressure variations.     

Relationships between DOC concentration,molecular size and fluorescence properties of DOM in a stream

The patterns of dissolved organic matter (DOM) fluorescence properties were examined in a Precambrian shield stream over a seven-month field study. Unique spatial and temporal patterns of simultaneous changes were observed in dissolved organic carbon concentration (DOC), humic-like fluorescence intensity, maximum excitation and emission wavelengths and fluorescence index (the ratio of the emission intensity at a wavelength of 450 nm to that at 500 nm at an excitation wavelength of 370 nm). The spatial change indicates the alteration of DOM along the length of the stream, and temporal change corresponded to a drought event in August. In contrast to humic-like fluorescence, the protein-like fluorescence shows considerable variability, suggesting its ephemeral nature. There were strong relationships between humic-like fluorescence intensity, fluorescence index, maximum Ex/Em wavelengths, DOC concentration and molecular size of DOM. This study has significant implications to the understanding of the nature and biogeochemical cycling of DOM.     

Effects of water chemistry and concentrations of dissolved organic matter on its fluorescence characteristics and molecular conformation

Previous studies showed that water chemistry and concentrations of dissolved organic matter (DOM) could affect its molecular conformation and binding characteristics with hydrophobic organic contaminants (HOCs). However, the conformational change of DOM resultant from water chemistry and concentrations of DOM was not extensively investigated; therefore, the contradictory reports regarding the binding property with HOCs were available in literature. In this study, the effects of ionic strength, pH and DOM concentrations on the fluorescence properties of two humic acids (HA), namely Fluka HA and Amherst HA, were investigated by three-dimensional excitation-emission matrix fluorescence spectroscopy (3DEEM) and steady-state fluorescence polarization (FP) techniques. The results not only corroborated previous observations obtained by other investigators, but revealed some new information about the fluorescence properties and molecular conformation of the humic acids under different water chemistry and DOM concentration conditions, which could shed light on its binding mechanisms and binding properties with HOCs.     

Application of excitation emission matrix fluorescence monitoring in the assessment of spatial and seasonal drivers of dissolved organic matter composition: Sources and physical disturbance controls

The environmental dynamics of dissolved organic matter (DOM) were characterized for a shallow, subtropical, seagrass-dominated estuarine bay, namely Florida Bay, USA. Large spatial and seasonal variations in DOM quantity and quality were assessed using dissolved organic C (DOC) measurements and spectrophotometric properties including excitation emission matrix (EEM) fluorescence with parallel factor analysis (PARAFAC). Surface water samples were collected monthly for 2 years across the bay. DOM characteristics were statistically different across the bay, and the bay was spatially characterized into four basins based on chemical characteristics of DOM as determined by EEM-PARAFAC. Differences between zones were explained based on hydrology, geomorphology, and primary productivity of the local seagrass community. In addition, potential disturbance effects from a very active hurricane season were identified. Although the overall seasonal patterns of DOM variations were not significantly affected on a bay-wide scale by this disturbance, enhanced freshwater delivery and associated P and DOM inputs (both quantity and quality) were suggested as potential drivers for the appearance of algal blooms in high impact areas. The application of EEM-PARAFAC proved to be ideally suited for studies requiring high sample throughput methods to assess spatial and temporal ecological drivers and to determine disturbance-induced impacts in aquatic ecosystems.     

Spatial Variation in the Optical Properties of Dissolved Organic Matter (DOM) in Lakes on the Canadian Precambrian Shield and Links to Watershed Characteristics

In the present study, we explored the use of various optical parameters to detect differences in the composition of the dissolved organic matter (DOM) in a set of lakes that are all located on the Canadian Precambrian Shield, but within which Cu and Ni speciation predictions were previously shown to diverge from measured values in some lakes but not in others. Water samples were collected with in situ diffusion samplers in 2007 (N = 18 lakes) and 2008 (N = 8 lakes). Significant differences in DOM quality were identified between the sampling regions (Rouyn-Noranda, Québec and Sudbury, Ontario) and among lakes, based on dissolved organic carbon concentrations ([DOC]), specific UV absorbance (SUVA₂₅₄), fluorescence indices (FI), and excitation–emission matrix (EEM) fluorescence measurements. Parallel factor analysis (PARAFAC) of the EEM spectra revealed four components, two of which (C3, oxidized quinone fluorophore of allochthonous origin, and C4, tryptophan-like protein fluorescence of autochthonous origin) showed the greatest inter-regional variation. The inter-lake differences in DOM quality were consistent with the regional watershed characteristics as determined from satellite imagery (e.g., watershed-to-lake surface area ratios and relative percentages of surface water, rock outcrops vegetative cover and urban development). Source apportionment plots, built upon PARAFAC components ratios calculated for our lakes, were used to discriminate among DOM sources and to compare them to sources identified in the literature. These results have implications for other areas of research, such as quantifying lake-to-lake variations in the influence of organic matter on the speciation of trace elements in natural aquatic environments.     

Airborne Laser-Induced Fluorescence (LIF) Light Detection and Ranging (LiDAR) for the Quantification of Dissolved Organic Matter Concentration in Natural Waters

Analysis of dissolved organic matter (DOM) concentration and composition is essential to quantifying biological and chemical oxygen demand and atmosphere?Cocean heat flux exchange in natural waters. However, manual water sampling is costly and time consuming over large areas. The purpose of this research was to analyze the applicability of airborne laser-induced fluorescence light detection and ranging (LiDAR) for the detection of DOM in estuarine ecosystems impacted by agriculture. A fluorescence LiDAR system (Airborne Marine) (FLS-AM) was used to assess the DOM concentration of the Annapolis River and Basin, Nova Scotia, Canada, as well as three rivers and their estuaries in Prince Edward Island, Canada. Two FLS-AM flight missions were conducted in the summers of 2008 and 2009 and the resulting datasets were compared with spectral fluorescence signature (SFS DOM) and dissolved organic carbon (DOC) analysis of in situ water samples. Significant positive correlations were found at five of seven sites between the FLS-AM DOM and SFS DOM relationship which indicates that the FLS-AM sensor is a good surrogate for traditional sample collection of DOM data in estuaries in this region. Positive correlations were also found at all sites between FLS-AM DOM values and DOC. FLS-AM DOM patterns show that DOM values are significantly higher in rivers and estuaries that drain watersheds which are heavily impacted by agricultural practices. The results of this study show that the FLS-AM can be used efficiently as a general indicator for how estuaries are affected by runoff from agricultural watersheds in real time and thus reduce the requirement for traditional water sample collection and laboratory analysis methods.     

洱海沉积物孔隙水中溶解有机质的三维荧光光谱特征

文章应用三维荧光光谱技术对洱海沉积物孔隙水中的溶解有机质进行了研究。结果表明,所有样品均含有4个明显的荧光峰,其中A和C为类腐殖酸荧光,B和D为类蛋白荧光。荧光强度在沉积物-水界面特别强,在1cm处急剧下降,之后随着沉积深度呈上升趋势。孔隙水溶解有机质均具有强的类蛋白荧光,揭示了溶解有机质中含有大量色氨酸、酪氨酸等芳环结构的类蛋白物质,并且在早期成岩过程中随着沉积深度呈积累趋势;类蛋白荧光与类腐殖酸荧光之间具有一定的相关关系,r(A,C)值在0.94-1.79之间,随着沉积深度逐渐下降,r(D,B)值在0.9-1.75之间,与r(A,C)值极为接近,且随着沉积深度有着类似的变化趋势,说明在洱海沉积物孔隙水中,r(D,B)与r(A,C)之间具有一定的相关性。     

运用3DEEMs及荧光偏振方法研究pH、离子强度及浓度效应对腐殖酸荧光光谱特性的影响

利用三维荧光激发.发射光谱(3DEEMs)及荧光偏振法研究了3例腐殖酸和1例湖泊溶解有机物(DOM)在不同腐殖酸浓度、离子强度和pH条件下的荧光光谱特性.实验结果表明,随着浓度增大,各腐殖酸样的荧光强度增大,其中垃圾渗滤液腐殖酸和Pahokee泥炭腐殖酸的荧光峰出现红移.随着浓度进一步增大,腐殖酸的荧光偏振值增大,由此推断在此浓度范围内腐殖酸由于分子间的排斥作用使其构型出现伸展.离子强度增大导致腐殖酸及阿哈湖DOM的荧光强度降低.随着氯化钾(KCI)浓度增大,Fluka腐殖酸的荧光峰A蓝移,荧光峰B的荧光偏振值出现减小,推测是由于静电中和作用使其荧光基团发生卷曲造成的.离子强度对其余腐殖酸样和阿哈湖DOM的其他荧光特性没有明显的影响.总的来说,pH值的变化对腐殖酸和湖泊DOM的荧光特征的影响是很明显的.随着pH值增大,腐殖酸和湖泊DOM的荧光强度增强.而pH值减小时,Fluka腐殖酸和Pahokee泥炭腐殖酸的荧光峰(A峰)蓝移,当pH值降到5时,Fhka腐殖酸的荧光峰突然红移到最大,随后又继续蓝移;垃圾渗滤液腐殖酸和阿哈湖DOM的荧光峰位无明显的漂移.所有样品的荧光偏振值都减小(但阿哈湖DOM的A峰变化不大),但在pHi≤5时又增大,这种现象表明随着pH值降低,腐殖酸和湖泊DOM中有机大分子发生卷曲,但在pH≤5时由于羧基的质子化又以平面伸展构型出现在溶液中.