Photobleaching of chromophoric dissolved organic matter in natural waters: kinetics and modeling

The effects of monochromatic and polychromatic UV and visible (VIS) radiation on the optical properties (absorption and fluorescence) of chromophoric dissolved organic matter (CDOM) were examined for a Suwannee River fulvic acid (SRFA) standard and for water from the Delaware and Chesapeake Bays. The primary (direct) loss of absorption and fluorescence occurred at the irradiation wavelength(s), with smaller secondary (indirect) losses occurring outside the irradiation wavelength(s). The efficiency of both direct and indirect photobleaching decreased monotonically with increasing wavelength. Exposure to polychromatic light increased the CDOM absorption spectral slope (S), consistent with previous field measurements. An analysis of the monochromatic photobleaching kinetics argues that a model based on a simple superposition of multiple chromophores undergoing independent photobleaching cannot apply; this conclusion further implies that the absorption spectrum of CDOM cannot arise solely from a simple superposition of the spectra of numerous independent chromophores. The kinetics of CDOM absorption loss with the monochromatic irradiation were employed to create a simple, heuristic model of photobleaching. This model allowed us to examine the importance of the indirect photobleaching losses in determining the overall photobleaching rates as well as to model the photobleaching of natural waters under polychromatic light fields. Application of this model to natural waters closely predicted the change in the CDOM spectral shape caused by photodegradation. The time scale of this process was consistent with field observations acquired during the summertime for coastal waters in the Middle Atlantic Bight (MAB). The results indicate that the ratio of the photodegradation depth to the mixed layer depth is a key parameter controlling the rate of the photobleaching in surface waters.     

Estimating the diffuse attenuation coefficient from optically active constituents in UK marine waters

We report a study of the attenuation of submarine Photosynthetically Active Radiation (PAR) in relation to the concentrations of Optically Active Constituents (OACs) in a range of water types around the United Kingdom. 408 locations were visited between August 2004 and December 2005. The diffuse attenuation coefficient (K_d) was estimated from profiles of downwelling PAR. Concentrations of Suspended Particulate Matter (SPM) were measured gravimetrically and concentrations of phytoplankton chlorophyll (chl) were measured by fluorometrically. Chromophoric Dissolved Organic Matter (CDOM) was measured either by fluorescence or as its proxy, salinity.     

Exudation and decomposition of chromophoric dissolved organic matter (CDOM) from some temperate macroalgae

The quantity of chromophoric or coloured dissolved organic matter (CDOM) released by eleven species of intertidal and sub-tidal macroalgae commonly found on UK shores was investigated. The subsequent breakdown of CDOM was also measured by exposing collected CDOM samples to light and dark conditions for over two weeks. CDOM absorption properties were compared at a fixed wavelength of 440 nm and across two integrated wave - bands; UV-A (400–315 nm) and UV-B (315–280 nm). Absorption spectra of macroalgal CDOM samples were typically characterized by peaks and shoulders in the UV bands, features which were species specific. The spectral slope, derived using the log-linear method, proved to be very specific to the species and to the effect of light. Slope measurements ranged from 0.010 to 0.027 nm⁻¹, in the range of normal seawater values. Significantly more CDOM was produced by algae which were illuminated, providing evidence for a light driven exudation mechanism. Averaged across all species, exudation in the dark accounted for 63.7% of that in the light in the UV-B band. Interspecific differences in exudation rate encompassed an order of magnitude, with the highest absorption measurements attributable to brown algae. However, some brown algae produced considerably less CDOM (e.g. Pelvetia canaliculata), which were more comparable to the green and red species. Over an exposure time of 16 days, significant photochemical degradation of CDOM was observed using a natural summer sunlight regime, showing that natural solar radiation could be an important removal mechanism for newly produced algal CDOM. Though the most obvious effect was a decrease in absorption, photo-bleaching also caused a significant increase in the spectral slope parameter of 0.004 nm⁻¹.     

长江口外海水中有色溶解有机物（CDOM）的光吸收特性

基于2008年5、11月2次调查数据,研究了长江口邻近海域水体有色溶解有机物（CDOM）的光吸收特性及其时空分布特征,探讨了CDOM含量、光谱斜率Sg值及其与特征波长下吸收系数a（440）的关系.结果表明,春季该海域有色溶解有机物的吸收系数a（440）的范围为2.232~8.671 m-1,平均值为4.523 m-1;秋季其吸收系数a（440）的变化范围为0.390~6.135 m-1,平均值为2.209 m-1.该水体CDOM吸收曲线基本呈指数衰减趋势.在400~440 nm波段内,春季其光谱斜率Sg值范围为0.002 0~0.014 2 nm-1,平均值为0.008 7 nm-1秋季的介于0.020 8~0.052 6 nm-1之间.平均值为0.037 5 nm-1.同时有色溶解有机物吸收系数a（440）与Sg值存在着较显著的负相关关系.     

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.     

基于遥感反演的浒苔绿潮暴发对有色溶解有机物与叶绿素时空分布特征的影响

浒苔的暴发会对水体生态环境产生巨大的影响, 对此进行遥感监测具有十分重要的意义。本文基于现场同步实测的有色溶解有机物(colored dissolved organic matter, CDOM)吸收系数、叶绿素浓度以及光谱数据建立遥感反演模型,再结合MODIS卫星影像提取山东半岛南侧近岸海域在各年份浒苔暴发前后CDOM与叶绿素浓度的时空分布特征。结果表明, 浒苔的消亡分解会在水体中产生大量的CDOM, 但浒苔的生长繁殖同样会消耗CDOM, 此外CDOM还受到浒苔暴发时期强烈的光降解作用。在各种因素的综合作用下, 研究区海域CDOM浓度在浒苔暴发时期微弱升高, 浒苔消亡后CDOM浓度则开始回落。浒苔在暴发期会抑制其他浮游微藻的生长, 使研究区海域叶绿素浓度有所降低, 而浒苔消亡后叶绿素浓度有所上升。水体中的叶绿素受多种生物地球化学因素的影响, 因此叶绿素浓度的降低与浒苔的暴发强度之间没有明确的相关性。遥感反演可以大范围快速地提取水体中各种要素的分布情况, 但就浒苔的暴发对海水中各要素的影响机制而言, 还需要结合各种生态环境因子进行综合分析。     

藻源性有机质对高原深水湖泊沉积物矿化作用的激发效应

湖泊营养水平提升,浮游植物快速增殖,大量藻类碎屑沉降到沉积物表面。藻屑作为新生不稳定有机质,对湖泊沉积物有机质(SOM)产生激发效应,影响湖泊沉积物碳循环过程。本文以深水湖泊抚仙湖南湖心沉积物为研究对象,采用优势种水华束丝藻(Aphanizomenon flos-aquae),进行不同浓度藻屑添加(×1倍组、×5倍组和×10倍组)的培养实验。应用碳同位素在线监测仪,探究藻屑添加对于SOM矿化作用的激发效应并预测可能产生的环境效应。结果表明：(1)添加的藻屑对上覆水和间隙水发光性溶解性有机质(CDOM)组成和性质产生影响,前期CDOM中类蛋白组分含量显著增加,但后期CDOM腐殖化程度升高。同时,藻屑的添加使二氧化碳(CO₂)释放量增大,蛋白酶活性和转化酶活性增强;(2)3个不同浓度的藻屑添加组均检测到不同程度激发效应,其中×1倍组和×5倍组对SOM矿化过程前期体现为正激发效应,最大值分别达到(12.18±0.65)和(26.60±9.14)μg/(mL ws),后期两个组别都转为负激发效应;×10倍组则在整个实验过程中均表现为负激发效应;(3)藻屑的添加使得间隙水易...     

海洋荧光溶解有机物研究进展

海洋荧光溶解有机物(FDOM)是海洋有色溶解有机物中可产生荧光的组分,其理化性质对于海洋上层的水色遥感、光化学以及浮游植物的生产力和生态系统结构与功能等都有重要影响。总结了FDOM的3种荧光光谱分析技术及其特点,重点对其两种主要成分(类腐殖质和类蛋白质荧光物质)的荧光特性、分布变化以及来源、分布变化及其去除等进行了全面细致的综述,阐述了研究FDOM的海洋学意义,并对今后有待深入研究的重点问题作了展望。     

三峡坝区水体吸收系数的特征研究

利用2007年11月在三峡坝区现场实测的水色要素吸收系数数据,对总颗粒物、浮游植物、CDOM的吸收系数特征进行了分析和研究。结果表明,对于三峡坝区区域的水体:(1)总颗粒物吸收光谱分布与非藻类的吸收光谱相似;(2)非藻类颗粒物的吸收系数随波长的变化分布接近指数衰减规律,且不同波段的吸收系数之间存在一定的关系;(3)多项式关系能较好的表达浮游植物吸收系数与叶绿素a浓度之间的关系;(4)分段函数能很好的表达CDOM的吸收系数特性,对500nm以下光谱的吸收呈现负指数衰减的规律,不同采样点拟合精度R2接近1;501—700nm波段范围的光谱曲线采用多项式能进行很好的拟和,且拟合精度R2达到95%以上。