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.     

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.     

Release of dissolved organic carbon from upland peat

This study examines the release of dissolved organic carbon (DOC) from upland peat during the period of the autumn flushing. Hydroclimatic conditions were monitored in conjunction with measurements of absorbance and the E4/E6 ratio of the stream draining an 11·4 km² upland peat catchment in northern England. During two months of monitoring the effects of 67 separate rainfall events were examined showing that:

• The peat behaves hydrologically as if it were a two end‐member system consisting of old, interevent, and new, event, water. Runoff is initiated by percolation excess of new water at the acrotelm–catotelm interface.
• The discharge of dissolved organic matter behaves like a three end‐member system with the between‐event water being low in DOC and storm events being characterized by two types of water. Initial runoff being characterized by new water rich in DOC that gives way to new water depleted in DOC. This transition can be ascribed to the runoff progressing from throughflow within the acrotelm progressing to saturation‐excess overland flow.
• Depletion of DOC during storm events is accompanied by a change in the character of the DOC as the E4/E6 ratio changes. This suggests that the decrease in DOC during events is the result of exhaustion of reserves rather than changes in the flowpaths being utilized by runoff.
• The amount of carbon released in any event is critically dependent upon the time between events during which oxidation processes generate a reservoir of available carbon. Production of available carbon in the catchment is as high as 4·5 g C per day per m³ of peat, suggesting a turnover rate of peat of the order of 42 years. Copyright © 2002 John Wiley & Sons, Ltd.

     

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.     

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...     

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.     

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.     

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.     

太湖藻源溶解性有机质光化学降解研究

蓝藻水华暴发过程会产生大量的溶解性有机质——藻源溶解性有机质(A-DOM);A-DOM的光化学降解影响其迁移转化和在湖泊中的功能.本研究从太湖藻华中提取A-DOM,利用三维荧光光谱-平行因子分析法(EEMsPARAFAC),研究A-DOM中各组分的光化学降解;再研究不同光照强度、溶解氧浓度、A-DOM浓度、波长对A-DOM的降解的影响.结果显示,A-DOM中含有4种EEMs-PARAFAC组分:C1(UVC类腐殖质)、C2(UVA类腐殖质)、C3(类色氨酸)和C4(类络氨酸),对总荧光强度的贡献比例分别为22.2%、8.6%、68.1%和1.1%.当DOC初始浓度为10 mg/L、反应温度为28℃、pH=8.0时,经500 W汞灯(391.7 W/m~2)光照12 h,A-DOM的总光化学降解率(以a_(355)计)为70.4%;荧光组分C1、C2和C3的降解率分别为96.1%、85.4%和99.2%,三者的光反应性为C3C1C2.条件控制实验显示溶解氧的增加和光强的增强均有助于A-DOM的降解;A-DOM光化学降解主要发生在紫外区,可见光不能使C1和C2得到降解.结果表明A-DOM的光化学降解速度较快,且能通过控制光强、照射光波长和引入溶解氧等条件控制降解速度.实验结果可为湖泊蓝藻水华暴发时的应急处理和保障饮用水安全提供理论依据.     

Dissolved oxygen as an indicator of bioavailable dissolved organic carbon in groundwater

Concentrations of dissolved oxygen (DO) plotted vs. dissolved organic carbon (DOC) in groundwater samples taken from a coastal plain aquifer of South Carolina (SC) showed a statistically significant hyperbolic relationship. In contrast, DO-DOC plots of groundwater samples taken from the eastern San Joaquin Valley of California (CA) showed a random scatter. It was hypothesized that differences in the bioavailability of naturally occurring DOC might contribute to these observations. This hypothesis was examined by comparing nine different biochemical indicators of DOC bioavailability in groundwater sampled from these two systems. Concentrations of DOC, total hydrolysable neutral sugars (THNS), total hydrolysable amino acids (THAA), mole% glycine of THAA, initial bacterial cell counts, bacterial growth rates, and carbon dioxide production/consumption were greater in SC samples relative to CA samples. In contrast, the mole% glucose of THNS and the aromaticity (SUVA(254)) of DOC was greater in CA samples. Each of these indicator parameters were observed to change with depth in the SC system in a manner consistent with active biodegradation. These results are uniformly consistent with the hypothesis that the bioavailability of DOC is greater in SC relative to CA groundwater samples. This, in turn, suggests that the presence/absence of a hyperbolic DO-DOC relationship may be a qualitative indicator of relative DOC bioavailability in groundwater systems.     

Sources of dissolved organic carbon during stormflow in a headwater agricultural catchment

Increasing dissolved organic carbon (DOC) concentrations have been reported during the last 15 years in streams from the United Kingdom, Northern Europe and North America. Identifying the sources of DOC and the controls of the delivery to the stream is important to understand the significance of these trends. This relies on the availability of observations of DOC dynamics during storm events, since much of the DOC export from soils to streams occurs during high flows. This study analyses DOC data for eight storm events during winter 2005–2006 in a small agricultural experimental catchment—the Kervidy‐Naizin experimental catchment—located in Western France. A four end‐member mixing approach was applied to the eight monitored storm events to identify DOC sources and quantify their respective contribution to DOC stream fluxes, using DOC, nitrate, sulphate and chloride as tracers. The results show that DOC concentrations in the stream at the outlet of this catchment increase markedly during storm events. The slope of the linear regression between DOC concentration and discharge was not constant for the eight events and depended on pre‐event hydrological conditions. Between 64 and 86% of the DOC that enter the stream during storms originated from the upper layers of the riparian wetland soils. The variation of the delivery of DOC seems to be controlled by hydrological processes only, the wetland soils acting as a non‐limiting store. Copyright © 2009 John Wiley & Sons, Ltd.     

有色溶解有机物吸收光谱模型对比

利用6种统计模型对吉林省石头口门水库、松花湖CDOM吸收光谱曲线(350-650nm)进行拟合,从统计F值大小和归一化残差两个角度均证明双曲线模型效果最好;采用15个波段范围拟合CDOM吸收均值光谱斜率S,单指数模型S值变化幅度较大,平均变异系数为12.41%;而双曲线模型S值相对稳定,变异系数为5.85%.将双曲线模型应用于生物光学模型,研究表明双曲线模型可以反映CDOM时空变化规律和物质组成;且双曲线模型拟合光谱斜率S值与CDOM特征波长吸收具有很好的负相关关系,呈幂指数递减,决定系数达0.8137.     

Dynamic stream network intermittence explains emergent dissolved organic carbon chemostasis in headwaters

Dissolved organic carbon (DOC) concentrations vary among headwaters, with variation typically decreasing with watershed area. We hypothesized that streamflow intermittence could be an important source of variation in DOC concentrations across a small watershed, through (a) temporal legacies of drying on organic matter accumulation and biotic communities and (b) spatial patterns of connectivity with DOC sources. To test these hypotheses, we conducted three synoptic water chemistry sampling campaigns across a 25.5‐km² watershed in south‐eastern Idaho during early spring, late summer, and late fall. Using changepoint analysis, we found that DOC variability collapsed at a consistent location (watershed areas ~1.3 to ~1.8 km²) across seasons, which coincided with the watershed area where variability in streamflow intermittence collapsed (~1.5 km²). To test hypothesized mechanisms through which intermittence may affect DOC, we developed temporal, spatial, and spatio‐temporal metrics of streamflow intermittence and related these to DOC concentrations. Streamflow intermittence was a strong predictor of DOC across seasons, but different metrics predicted DOC depending on season. Seasonal changes in the effects of intermittence on DOC reflected seasonal changes from instream to flowpath controls. A metric that captured spatial connectivity to sources significantly predicted DOC during high flows, when DOC is typically controlled by transport. In contrast, a reach‐scale temporal metric of intermittence predicted DOC during the late growing season, when DOC is typically controlled by instream processes and when legacy effects of drying (e.g., diminished biological communities) would likely affect DOC. The effects of intermittence on DOC extend beyond temporal legacies at a point. Our results suggest that legacy effects of intermittence do not propagate downstream in this system. Instead, snapshots of spatial patterns of intermittence upstream of a reach are critical for understanding spatial patterns of DOC through connectivity to DOC sources, and these processes drive patterns of DOC even in perennial reaches.     

A model of dissolved organic carbon concentrations in soil and stream waters

The release of dissolved organic carbon (DOC) into drainage waters was modelled using the hydrology of the Birkenes model of stream water chemistry and estimated parameters for the formation and decay of soluble organic matter in the soil. The model was first tested against soil water DOC concentrations over a three year period in the Loch Dee catchment in southwest Scotland. It predicted annual cycles in DOC at one site, but underestimated maximum DOC in the first year, overestimated in the following year, and predicted values very similar to the measured values in the third year. With small modifications to the parameters controlling organic matter addition and decay it successfully predicted DOC variations at two other soil water sites with smaller mean DOC. Further tests were made against short-term DOC variations in a stream draining a subcatchment of Loch Ard in west-central Scotland, using the same decay and addition parameters. Prediction of temporal variation was good, although predicted concentrations were about 25 per cent less than measured values. Considerable potential for the use of fully optimized models of DOC production in soil and stream waters is identified on the basis of these results.     

Jet drop enrichment of bacteria,virus, and dissolved organic material

Four parameters that control the enrichment of bacteria in jet drops are bubble scavenging, drop size, drop position in the jet set, and the type of bacteria. Without the scavenging of bacteria as a bubble rises through the water it is doubtful that the observed enrichment factors, EF, greater than 1000 could be obtained. There is a maximum in EF as a function of top jet drop size, and the EF decreases from the top to the bottom drop of the jet set. The efficiency by which bubbles scavenge bacteria varies with species. Presumably these parameters apply in some degree to the EF of virus in jet drops. Dissolved organic material in natural waters can adsorb to bubbles and contribute to a large EF in jet drops, but there is a feedback mechanism whereby changes in bubble surface free energy modify the jet drop-size distribution. However, there is reason to believe this will not significantly influence the jet drop-size distribution produced by bubbles in the sea.     

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.