Spectrophotometric discrimination of river dissolved organic matter

There is a need to be able to differentiate the dissolved organic matter (DOM) fraction in river waters. Research in the 1970s and 1980s has attempted to utilize both absorbance and fluorescence to distinguish between DOM fractions in river waters, but both were limited by the available technology. Total organic carbon content has, therefore, been widely used as a standard method of measuring DOM concentration, although it has little power to differentiate DOM fractions. Recent advances in fluorescence spectrophotometry enable rapid and optically precise analysis of DOM. Here, we show how a combination of both fluorescence and absorbance can be used to discriminate statistically between spatial variations of DOM in tributaries in a small catchment of the Ouseburn, NE England. The results of the discriminant analysis suggest that about 70% of the samples can be correctly classified to its tributary. Discriminant function 1 explains 60·8% of the variance in the data and the fulvic‐like fluorescence intensity has the largest absolute correlation within this function; discriminant function 2 explains a further 21·5% of the variance and the fulvic‐like fluorescence emission wavelength has the largest absolute correlation within this function. The discriminant analysis does not correctly classify all tributaries every time, and successfully discriminates between the different tributaries 70% of the time. Occasions when the tributary waters are less well discriminated are due to either episodic pollution events (at two sites) or due to tributaries that have strong seasonal trends in spectrophotometric parameters, which allows the sites to be misclassified. Results suggest that spectrophotometric techniques have considerable potential in the discrimination of DOM in rivers. Copyright © 2002 John Wiley & Sons, Ltd.     

高邮湖、南四湖和东平湖有色可溶性有机物来源组成特征

高邮湖、南四湖和东平湖作为南水北调东线枢纽湖泊,其水质状况对保障调水安全起到关键性作用本文运用三维荧光光谱平行因子分析法(EEMs-PARAFAC)分析了3个湖泊在不同水文情景下有色可溶性有机物(CDOM)吸收、荧光光谱特征以及荧光组分与主要水质参数的相关性,以探究3个湖泊CDOM来源组成特征结果表明,平行因子分析法解析CDOM三维荧光图谱,得到陆源类腐殖质C1、类色氨酸C2和类酪氨酸C3不同水文情景对高邮湖CDOM来源与结构组成影响较明显,丰水期其类腐殖质荧光强度显著大于枯水期(t-test,P<0.01),并且与a(254)呈正相关(R²=0.85,P<0.01),表明类腐殖质是CDOM主要部分,该荧光组分贡献率可达50%[F_maxC1/(F_maxC1+F_maxC2+F_maxC3)×100%],高邮湖受到入湖河流来水的影响较大,丰水期入湖口附近荧光强度明显高于其他水域东平湖和南四湖CDOM来源组成特征相似,丰水期东平湖和南四湖组分C2和C3显著低于枯水期(t-t...     

Patterns of dissolved organic matter in subarctic peatlands

Samples of water from poor to very rich fens in the Schefferville region of subarctic Quebec revealed strong spatial and temporal variations in dissolved organic carbon (DOC), ranging from 2 to 40 mg 1^?1. Concentrations of DOC tend to increase during the summer and decrease in the autumn, at most sites, which probably reflects increased plant tissue decomposition and higher rates of evapotranspiration. Principal components analysis revealed that DOC is strongly associated with Fe, NO^?₃-N and NO^?₂-N, but essentially independent of other chemical properties of the peat water, such as pH, Ca, Mg, K, P, and NH⁺₄-N. Based on observed concentrations of DOC and estimates of summer runoff (June to September), export of DOC from four peatlands ranges from 1·1 to 4·9 gCm^?2, with the lowest values for peatlands underlain by dolomite. Molecular weight fractionation of four samples revealed significant differences in the dissolved organic matter (DOM), with the largest fractions (GF/C to 10 000 nmw) being dominant in the more acid samples. The ratio of absorbance at 400 and 600 nm wavelengths (E₄:E₆) has been used as a simple indicator of differences in DOM type, ranging from 3 to 15. There is a strong seasonal pattern of increasing E₄:E₆ ratio during the summer at many sites, though this ratio is essentially independent of other chemical properties of peat waters.     

周村水库汛期暴雨中溶解有机物(DOM)的光谱特征及来源解析

运用三维荧光光谱（EEMs）技术结合平行因子分析法（PARAFAC）,对周村水库夏季两场暴雨不同降雨历时以及分子量的溶解有机物光谱特征和来源进行分析.结果表明：周村水库不同暴雨荧光光谱中出现了5种组分,分别为类腐殖质（C1、C2）、可见区富里酸（C3）和类蛋白（C4、C5）;相关性分析显示C1与C2、C3、C4以及C5具有显著的相关性,C2与C3具有显著的相关性,C3与C4以及C5具有显著的相关性;同一分子量下的雨水有机质总荧光强度以及各组分荧光强度随着降雨历时的增加均呈下降趋势,并且在各个历时和分子量间差异明显;同一降雨历时下,第一场暴雨总荧光强度随着分子量的减少而增加,第二场暴雨总荧光强度随着分子量的减少而减少;两场暴雨都呈现自生源的特征,其中第一场暴雨具有以陆源输入为主的特征;组分C1和C3与水质参数硝态氮、氨氮、总氮以及有机碳呈显著相关性.通过对暴雨在不同降雨历时以及分子量DOM光谱特征研究,可以进一步分析水库外源输入的天然有机质特征,为水库水质管理提供技术支持.     

典型湖泊天然有机质与四环素的相互作用

采用荧光滴定法研究四环素(tetracycline,TC)与太湖溶解性有机质(dissolved organic matter,DOM)和玄武湖DOM的相互作用.三维荧光光谱结合平行因子分析显示,2个湖泊的DOM含有3个荧光组分:类富里酸组分C1、类色氨酸组分C2和类络氨酸组分C3.其中C2的荧光强度远高于C1和C3,是DOM的主要荧光组成.3个荧光组分与TC发生了不同程度的静态猝灭,特别当TC浓度为45.5μmol/L时,类蛋白组分的荧光强度完全被猝灭(100%),并且猝灭作用改变了DOM分子的微环境极性.同步荧光光谱联合二维相关图谱进一步表明类色氨酸组分优先和TC发生猝灭作用,其次为类络氨酸组分和类富里酸组分.Ryan-Weber方程适于拟合DOM与TC的猝灭过程,2个湖泊的DOM中3个荧光组分的络合常数lg K值范围为5.05~5.85,大小顺序为C2C3C1.因此,类蛋白组分为主的DOM对TC的络合作用大于类腐殖组分为主的DOM,影响抗生素在湖泊水体中的生物有效性和生态毒性.     

溶解性有机质与水生生物的直接相互作用研究进展

溶解性有机质广泛存在于天然水体中,具有重要的生态与环境意义.然而在环境科学领域内,天然水体中的溶解性有机质长期以来仅仅被作为惰性的吸附剂对待,其自身的与生物的直接作用却一直被忽视.近年来,越来越多的研究证据表明溶解性有机质自身即具有生物效应.它能在生物表面吸附.并影响细胞膜的电化学性质与膜渗透性,能被生物吸收,进而诱导...     

Effect of organic matter source and salinity on dissolved organic matter isolation via ultrafiltration and solid phase extraction

In this study, samples were taken from three contrasting freshwater sources and amended with salt in order to determine the influence of salinity and dissolved organic matter (DOM) composition on DOM recovery via ultrafiltration and solid phase extraction (SPE) with C₁₈ disks. Salt addition caused variable recovery of DOM when using C₁₈ SPE, and ultraviolet–visible spectroscopic characterization of the extracted material showed spectral responses that varied among sample sources. In contrast, increasing sample salinity from 0 to 30 ppt consistently caused a 15–25% reduction in the amount of high molecular weight DOM isolated by ultrafiltration for both dissolved organic carbon (DOC) and chromophoric DOM (CDOM), regardless of DOM composition. We hypothesize that a change in conformation (such as coiling or disaggregation) of DOM molecules occurs in the presence of salt, allowing them to pass through the ultrafiltration membrane and thereby decreasing the DOM retained by ultrafiltration. These results are important because they demonstrate that changes in salinity can influence DOM recovery in estuaries. Interpretation of DOM characteristics along estuarine gradients needs to account for potential artifacts introduced by sample isolation techniques.     

The freshwater dissolved organic matter fluorescence–total organic carbon relationship

The fluorescent properties of dissolved organic matter (DOM) enable comparisons of humic‐like (H‐L) and fulvic‐like (F‐L) fluorescence intensities with dissolved organic carbon (DOC) in aquatic systems. The fluorescence‐DOC relationship differed in gradient, i.e. the fluorescence per gram of carbon, and in the strength of the correlation coefficient. We compare the fluorescence intensity of the F‐L and H‐L fractions and DOC of freshwater DOM in north Shropshire, England, featuring a river, wetland, spring, pond and sewage DOM sources. Correlations between fluorescence and DOC varied between sample sites. Wetland water samples for the F‐L peak gave the best correlation, r = 0·756; the lowest correlation was from final treated sewage effluent, r = 0·167. The relationship between fluorescence and DOC of commercially available International Humic Substances Society standards were also examined and they generally showed a lower fluorescence per gram of carbon for the F‐L peak than the natural samples, whereas peat wetland DOM gave a greater fluorescence per gram of carbon than river DOM. Here, we propose the strength of the fluorescence–DOC correlation to be a useful tool when discriminating sources of DOM in fresh water. Copyright © 2007 John Wiley & Sons, Ltd.     

Determination of dissolved organic matter in streamwater using visible spectrophotometry

Absorbance at 360 nm was measured on 44 filtered streamwater samples of different dissolved organic matter (DOM) contents. A regression equation of DOM on absorbance predicted DOM with a standard error of estimate of 1.26 mgl^?1, Use of a published equation relating dissolved organic carbon (DOC) to absorbance gave DOC values for the samples which were consistent with measured DOM. The method offers considerable potential for rapid quantification of dissolved organic matter concentrations in streamwater.     

云南高原湖泊有色可溶性有机物和颗粒物光谱吸收特性

云南高原湖泊是我国湖泊分布最密集的五大湖群之一,不但湖泊数量众多而且类型多样.由于湖泊所处位置海拔较高,容易受只益增强UV-B辐射影响.通过对云南高原34个湖泊有色可溶性有机物和颗粒物吸收测定,分析其光谱吸收特性及对总吸收的贡献,有利于深刻理解紫外辐射在高原湖泊内衰减.不同湖泊间CDOM吸收差异明显,其大小与水体营养盐状况相关,CDOM吸收系数与水体总氮存在显著正相关.增加背景项的指数函数模型能最好模拟CDOM光谱吸收.除在浮游植物浓度非常高的杞麓湖、听湖、星云湖,颗粒物吸收系数在675nm附近存在一个吸收蜂外,其它湖泊总颗粒物光谱吸收大致随波长的增加吸收系数逐渐降低,呈现非色素颗粒物光谱吸收特征,整体上颗粒物吸收以非色素颗粒物为主.CDOM对总吸收的贡献主要集中在600nm以下波长,尤其是400nm以下的紫外波段,其在紫外波段(350-400nm)的贡献明显要大于光合有效辐射波段(400-700nm)(ANOVA,P<0.001).特别对于透明度SD≥1.0的清澈型湖泊,CDOM吸收对紫外辐射衰减的贡献更大,其吸收很大程度上决定了紫外辐射的影响深度.     

太湖沿岸水体CDOM吸收光谱特性

有色可溶性有机物(CDOM)吸收光谱特性研究对于水色定量遥感反演具有重要作用.通过2007年6月10日至6月18日太湖沿岸68个CDOM吸收光谱曲线和水质参数实测数据,分析了CDOM吸收光谱曲线特征以及ag(440)、Sg值及其相关关系等,结果表明:太湖沿岸水体CDOM吸收光谱曲线表现为两种类型,贡湖湾CDOM吸收系数明显高于太湖其他沿岸水域,ag(440)最高值即出现在贡湖湾;同时,梅梁湾、贡湖湾、镇湖湾、光富湾等ag(440)高于沿岸水体平均值,而南部3个湖湾皆低于平均值.另外,贡湖湾Sg值较小,且与ag(440)呈现出较好的关系;而沿岸其它水体Sg值与ag(440)虽然呈现负相关,但关系不明显.这对于了解太湖水体CDOM特件以及定量反演有一定的意义和作用.     

长江中游湖泊CDOM光学特性及其空间分布对比

根据2007年秋季洪湖、东湖和梁子湖的调查结果,分析了长江中游3个典型湖泊CDOM光学特性及其空间分布差异.结果表明:(1)CDOM吸收系数在洪湖最高,梁子湖最低;(2)在洪湖,CDOM吸收系数受陆源影响较大,与悬浮泥沙浓度呈现较好正相关关系,而在梁子湖,CDOM吸收系数主要受到浮游植物降解贡献,与叶绿素浓度具有显著的正相关关系;(3)洪湖与东湖指数函数斜率S值变化不大;梁子湖CDOM吸收系数空间分布差异较大,指数函数斜率S值与400nm波段CDOM吸收系数ag(400)显著负相关.在建立梁子湖CDOM遥感反演模型时,应引入上述指数甬数斜率S值与400nm波段CDOM吸收系数之间的线性函数,对CDOM吸收系数的指数模型进行优化.     

The regime of dissolved gases and organic matter in Selenga basin rivers

The gas regime and active reaction of water in Selenga basin rivers are analyzed. It is shown that, in the lower reaches of the Selenga and Uda rivers, which experience the highest anthropogenic impact, the minimal values of hydrogen index were recorded in under-ice period, while in the rivers of Chikoi, Khilok, Dzhida, and Temnik, during spring flood and summer freshets. The concentrations of organic substances are heterogeneous and vary widely under the effect of matter input with major tributaries and wastewater discharge from GOS. It has been established that the concentrations of readily oxidizable organic substances in 28–33% of the taken samples are above the established standards on maximal allowable concentrations in the period of open river channels. In spring and autumn, the organic matter in the rivers of the basin is mostly represented by soil terrigenous material.     

Glacial to Holocene terrigenous organic matter input to sediments from Orca Basin, Gulf of Mexico — A combined optical and biomarker approach

In this study we assessed changes in the contribution of terrigenous organic matter (OM) to the Gulf of Mexico over the course of the last deglaciation (the last 25 kyr). To this end, we combined optical kerogen analyses with bulk sedimentary, biomarker, and compound-specific carbon isotope analyses. Samples were obtained from core MD02-2550 from Orca Basin (2249 m water depth at 26°56.77N, 91°20.74W) with temporal resolution ranging from multi-decadal to millennial-scale, depending on the proxy. All proxies confirmed larger terrigenous input during glacial times compared to the Holocene. In addition, the kerogen analyses suggest that much of the glacial OM is reworked (at least 50% of spores and pollen grains and 40% of dinoflagellate cysts). The Holocene sediments, in contrast, contain mainly marine OM, which is exceptionally well preserved. During the deglaciation, terrigenous input was generally high due to large meltwater fluxes, whereby discrepancies between different proxies call for additional influences, such as the change in distance to the river mouth, local productivity changes, and hydrodynamic particle sorting. It is possible that kerogen particles and the terrigenous biomarkers studied here represent distinct pools of land-derived OM with inputs varying independently.